DK164860B - ANALOGY PROCEDURE FOR PREPARING BENZOXAZIN-2-ONER - Google Patents
ANALOGY PROCEDURE FOR PREPARING BENZOXAZIN-2-ONER Download PDFInfo
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- DK164860B DK164860B DK195583A DK195583A DK164860B DK 164860 B DK164860 B DK 164860B DK 195583 A DK195583 A DK 195583A DK 195583 A DK195583 A DK 195583A DK 164860 B DK164860 B DK 164860B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/18—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with hetero atoms directly attached in position 2
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- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P7/00—Drugs for disorders of the blood or the extracellular fluid
- A61P7/02—Antithrombotic agents; Anticoagulants; Platelet aggregation inhibitors
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- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
Description
DK 164860 BDK 164860 B
I offentliggjort europæisk patentansøgning nr. 3.771 beskrives carbostyril- og oxindolderivater, der foruden en positiv inotrop virkning især opviser antithrombo-tiske egenskaber.Published European Patent Application No. 3,771 discloses carbostyril and oxindole derivatives which, in addition to a positive inotropic effect, exhibit in particular antithrombotic properties.
^ Det er nu blevet fundet, at hidtil ukendte benzo- xazin-2-oner med den almene formel I: R R9 Rt vi* R6 \ hvori A er et svovlatom, en SO-, S00-, R-N=S-grupoe eller 15 1 R-N=S0-gruppe, i hvilke R er et hydrogenatom, en ligekædet alkanoylgruppe med 1-9 carbonatomer, en pivaloylgruppe, en benzoyl-gruppe, der eventuelt er substitueret med et fluor-, chlor- eller bromatom eller med en methyl-, 20 ethyl-, isopropyl-, t-butyl- eller acetoxygruppe, en benzoylgruppe substitueret med to fluoratomer, to chloratomer eller to eller tre methylgrupper, en phenylsulfonylgruppe, der eventuelt er substitueret med en methylgruppe eller et fluor-, chlor-25 eller bromatom, en naphthoyl-, thenoyl, pyridi- noyl-, hydroxysulfonyl-, methansulfonyl-, ethanol- sulfonyl-, pentamethylphenylsulfonyl-, methoxy- carbonyl-, ethoxycarbonyl-, n-propoxycarbonvl, isopropoxycarbonyl-, benzyloxycarbonyl-, amino-30 carbonyl-, methylammocarbonyl eller dimethylamino-carbonylgruppe, D er en ligekædet eller forgrenet alkylengruppe med 2-6 carbonatomer, R. er en eventuelt med en phenylgruppe substitueret al- 3 5 kylgruppe substitueret alkylgruppe med 1-3 carbon- 2It has now been found that novel benzoxazin-2-ones of the general formula I: R R9 Rt vi * R6 \ wherein A is a sulfur atom, an SO, S00, RN = S group, or 15 1 RN = SO group in which R is a hydrogen atom, a straight chain alkanoyl group having 1-9 carbon atoms, a pivaloyl group, a benzoyl group optionally substituted with a fluoro, chloro or bromine atom or with a methyl, An ethyl, isopropyl, t-butyl or acetoxy group, a benzoyl group substituted with two fluorine atoms, two chlorine atoms or two or three methyl groups, a phenylsulfonyl group optionally substituted by a methyl group or a fluorine, chlorine or bromine atom, a naphthoyl, thenoyl, pyridinoyl, hydroxysulfonyl, methanesulfonyl, ethanol sulfonyl, pentamethylphenylsulfonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, benzyloxycarbonyl, benzyloxycarbonyl, or dimethylamino carbonyl group, D is a straight or branched alkylene is a group optionally substituted with a phenyl group, alkyl group substituted alkyl group having 1-3 carbon atoms.
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atomar eller en phenylgruppe, idet den ovenfor nævnte phenylkerne i hvert tilfælde kan være substitueret med en alkvlgruppe med 1-4 carbonatomer, et halogenatom, en alkoxygruppe med 1-3 carbonatomer, en hydroxy-, 5 cyclohexyl- eller phenylgruppe, en aminogruppe'eller en alkanoylaminogruppe med 1-3 carbonatomer; en alkyl-gruppe med 4-8 carbonatomer, en cycloalkylgruppe med 3-7 carbonatomer, en med alkylgrupper med 1-4 carbonatomer, alkoxygrupper med 1-3 carbonatomer og/.éller 10 halogenatomer, di- eller trisubstitueret phenylgruppe eller mono- eller disubstitueret hydroxyphenyl- eller aminophenylgruppe, idet herved substituenterne på phenylkernen i hvert tilfælde kan være ens eller forskellige, en eventuelt med en eller to methylgrupper 15 substitueret pyridyl- eller pyriminidylgruppe, en pyridyl-N-oxid-, ethylpyridyl-, ethylpyrimidinyl-, propylpyrimidinyl-, diethylpyrimidinyl-, pyrazinyl-, pyrida2inyl-, pyrazolyl-, imidazolyl-, triazolyl-, indolyl-, indazolyl, chinolyl-, isochinolyl, china-20 zolinyl-, benzimidazolyl- eller benzthiazolylgruppe, R2 og R3, der kan være ens eller forskellige, er hydrogen-atomer, phenylgrupper, alkylgrupper med 1 til 6 carbonatomer eller cycloalkylgrupper med 3 til 7 carbonatomer, 25 R4 er et hydrogenatom eller en alkylgruppe med 1 til 3 carbonatomer, R5 er et hydrogen- eller halogenatom, en nitro- eller alkylgruppe med 1 til 3 carbonatomer, og *6 er et hydrogen- eller halogenatom eller en alkylgruppe 30 med 1 til 3 carbonatomer, opviser værdifulde farmakologiske egenskaber især overlegne antithrombotiske virkninger.atom or a phenyl group, the above-mentioned phenyl nucleus being substituted in each case by an alkyl group having 1-4 carbon atoms, a halogen atom, an alkoxy group having 1-3 carbon atoms, a hydroxy, cyclohexyl or phenyl group, an amino group or the like. an alkanoylamino group having 1-3 carbon atoms; an alkyl group of 4-8 carbon atoms, a cycloalkyl group of 3-7 carbon atoms, one of alkyl groups of 1-4 carbon atoms, alkoxy groups of 1-3 carbon atoms and / or 10 halogen atoms, di- or trisubstituted phenyl group or mono- or disubstituted hydroxyphenyl or aminophenyl group, whereby the substituents on the phenyl nucleus may in each case be the same or different, optionally substituted with one or two methyl groups, pyridyl or pyriminidyl group, a pyridyl-N-oxide, ethylpyridyl, ethylpyrimidinyl, propylpyrimidinyl, diethylpyrimidinyl, pyrazinyl, pyridazinyl, pyrazolyl, imidazolyl, triazolyl, indolyl, indazolyl, quinolyl, isoquinolyl, quinazolinyl, benzimidazolyl or benzthiazolyl group, R 2 and R are hydrogen atoms, phenyl groups, alkyl groups of 1 to 6 carbon atoms or cycloalkyl groups of 3 to 7 carbon atoms, R 4 is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, R 5 is a hydrogen or halogen atom, a nitro or alkyl group of 1 to 3 carbon atoms, and * 6 is a hydrogen or halogen atom or an alkyl group 30 of 1 to 3 carbon atoms, exhibit valuable pharmacological properties, especially superior antithrombotic effects.
I overensstemmelse hermed angår opfindelsen en analogifremgangsmåde til fremstilling af de ovenfor defi-55 nerede benzoxazin-2-oner med formel I; fremgangsmåden er ejendommelig ved det i kravets kendetegnende del angivne.Accordingly, the invention relates to an analogous process for the preparation of the above-defined benzoxazin-2-ones of formula I; the process is peculiar to the characterizing part of the claim.
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For de ved definitionen af grupperne A, D og til R6 ovenfor nævnte betydninger kommer f.eks. for A betydningen et svovlatom, en sulfoxid-, sulfonyl-, sulf-imino-, N-£ormy1-sulfimino-, N-acetyl-sulfimino-, 5 N-propionyl-sulf imino-, N-pi valoyl-sulf imino-, N-pentanoyl-sulf imino-, N-hexanoyl-sulf imino-, N -heptanoy 1-sulf imino-, N-octanoy 1- sul f imino-, N-nonanoy 1-sulf imino-, N-methoxyacetyl-sulf imi no-, N-methoxypropionyl-sulfimino-, N-benzoyΙ-ΙΟ sulfimino-, N-fluorbenzoy1-sulfimino-, N-chlor- benzoy1-sulfimino-, N-brombenzoy1-sulfimino-, N-methylbenzoyl-sulfimino-, N-ethyl-benzoyl-sulf-imino-, N-isopropylbenzoy1-sulfimino-, N-tert. butylbenzoy 1-sulf imino-, N-difluorbenzoyl-sulf-15 imino-, N-dichlorbenzoyl-sulf imino-, N-dimethyl- benzoyl-sulf imino-, N-trimethy lbenzoyl-sulf imi no-, N-naphthoy 1-sulf imino-, N-pyridinoyl-sulf-imino-, N-thenoyl-sulf imino-, N-acetoxy-benzoyl-sulfimino-, N-hydroxysulfony1-sulfimino-, N-me-20 thansulfonyl-sulfimino-, N-ethansulfonyl-sulfimi no-, N-phenylsulfonyl-sulfimino-, N-methylphenyl-sulfonyl-sulfimino-, N-fluorphenyl-sulfonyl-sulf-imino-, N-chlorphenylsulfonyl-sulfimino-, N-brom-pheny lsu 1 f onyl-s ul f imino-, N-pentamethylphenyl-25 sulfonyl-sulfimino-, N-naphthylsulfonyl-sulfimi- no-, N-methoxycarbonyl-sulfimino-, N-ethoxycarbo-nyl-sulfimino-, N-propoxycarbonyl-sulfimino-, N-isopropoxycarbonyl-sulf imino-, N-benzyloxycarbo-nyl-sulfimino-, N-aminocarbonyl-sulfimino-, N-me-30' thylaminocarbonyl-sulfimino-, N-dimethylaminocar- bonyl-sulfimino-, sulfoximino-, N-formyl-sulfoxi-mino-, N-acetyl-sulfoximino-, N-propionyl-sulf-oximino-, N-pivaloyl-sulfoximino-, N-pentanoyl-sulfoximino-, N-hexanoyl-sulfoximino-, N-heptano-35 yl-sulfoximino-, N-nonanoy1-sulfoximino-, N-me thoxyacetyl-sulf oximino-, N-methoxypropionyl-sulfoximino-, N-benzoyl-sulfoximino-, N-fluor-benzoy 1-sulf oximino-, N-chlorbenzoyl-sulfoximi- 4For the meanings mentioned in the definitions of groups A, D and to R6 above, e.g. for A is a sulfur atom, a sulfoxide, sulfonyl, sulf imino, N-formyl-sulfimino, N-acetyl-sulfimino, N-propionyl-sulf imino, N-pi valoyl-sulf imino, , N-pentanoyl-sulf imino-, N-hexanoyl-sulf imino-, N -heptanoy-1-sulf imino-, N-octanoy-1-sulfin imino-, N-nonanoy 1-sulf imino-, N-methoxyacetyl-sulf imi no-, N-methoxypropionyl-sulfimino-, N-benzoyl-ΙΟ-sulfimino-, N-fluorobenzoyl-sulfimino-, N-chlorobenzoyl-sulfimino-, N-bromobenzoyl-sulfimino-, N-methylbenzoyl-sulfimino-, N -ethyl-benzoyl-sulf-imino-, N-isopropylbenzoyl-sulfimino-, N-tert. butyl benzoyl 1-sulf imino-, N-difluorobenzoyl-sulf-imino-, N-dichlorobenzoyl-sulf imino-, N-dimethylbenzoyl-sulf imino-, N-trimethylbenzoyl-sulf imino-, N-naphthoy-1 sulf imino-, N-pyridinoyl-sulf-imino-, N-thenoyl-sulf imino-, N-acetoxy-benzoyl-sulfimino-, N-hydroxysulfonyl-sulfimino-, N-methanesulfonyl-sulfimino-, N-ethanesulfonyl -sulfimino, N-phenylsulfonyl-sulfimino, N-methylphenyl-sulfonyl-sulfimino, N-fluorophenyl-sulfonyl-sulf-imino-, N-chlorophenylsulfonyl-sulfimino, N-bromo-phenylsulfonyl-s ul of imino, N-pentamethylphenylsulfonylsulfimino-, N-naphthylsulfonylsulfimino-, N-methoxycarbonylsulfimino-, N-ethoxycarbonylsulfimino-, N-propoxycarbonylsulfimino-, N-isopropoxycarbonyl -sulf imino-, N-benzyloxycarbonylsulfimino-, N-aminocarbonylsulfimino-, N-methylethylcarbonylsulfimino-, N-dimethylaminocarbonylsulfimino-, sulfoxymino-, N-formylsulfoxy- mino-, N-acetyl-sulfoxymino, N-propionyl-sulfoxymino, N-pivaloyl-sulfoxymino, N-pentanoyl-sulfox imino, N-hexanoyl-sulfoxymino, N-heptanoyl-sulfoxymino, N-nonanoyl-sulfoxymino, N-methoxyacetyl-sulfoxymino, N-methoxypropionyl-sulfoxymino, N-benzoyl-sulfoxymino, N-fluoro-benzoyl 1-sulfoxymino-, N-chlorobenzoyl-sulfoxime-4
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no, N-brombenzoyl-sulfoximino-, N-methylbenzoyl-sulfoximino-, N-ethylbenzoyl-sulfoximino-, N-isopropylbenzoyl-sulfoximino-, N-tert.butyl-benzoyl-sulfoximino-, N-difluorbenzoyl-sulfoximi-5 no-, N-dichlorbenzoyl-sulfoximino-, N-dimethyl- benzoyl-sulfoximino-, N-trimethylbenzoyl-sulf-oximino-, N-naphthoyl-sulfoximino-, N-pyridinoyl-sulfoximino-, N-thenoyl-sulfoximino-, N-acetoxy-benzoyl-sulfoximino-, N-hydroxy-sulfoximino-, N-10 methansulfonyl-sulfoximino-, N-ethansulfonyl- sulfoximino-, N-phenylsulfonylsulfonyl-sulfox~ imino-, N-methylphenylsulfonyl-sulfoximino-, N-fluorphenylsulfonyl-sulfoximino-, N-chlorphenyl-sulfony1-sulfoximino-, N-bromphenylsulfonyl-15 sulfoximino-, N-pentamethylphenyl-sulfoximino-, N-naphthylsulfonyl-sulfoximino-, N-methoxycarbo-nyl-sulfoximino, N-ethoxycarbonyl-sulfoximino-, N-propoxycarbonyl-sulfoximino-, N-isopropoxy-car-bony1-sulfoximino-, N-benzyloxycarbonyl-sulfoxi-20 mino-, N-aminocarbonyl-sulfoximino-, N-methylami- nocarbonyl-sulfoximino- eller N-dimethylaminocar-bonyl-sulfoximinogruppe, for D en ethylen-, n-propylen-, n-butylen-, n-penty-len, n-hexylen-, 1-methyl-ethylen-, 2-methyl-25 ethylen-, 1-methyl-n-propylen-, 2-methyl-n-propy- len-, 3-methyl-n-propylen-, 1-methyl-n-butylen-, 2-methyl-n-butylen-, 3-methyl-n-butylen-, 4-me-thyl-n-butylen-, 1-methyl-n-pentylen, 2-methyl-n-pentylen-, 3-methyl-n-pentylen-, 4-methyl-n-30 pentylen-, 5-methyl-n-pentylen-, 1,1-dimethyl- ethylen-, 1,2-dimethyl-ethylen-, 2,2-dimethyl-ethylen-, 1,1-dimethyl-n-propylen-, 2,2-dimethyl-n-propylen-, 3,3-dimethyl-n-propylen-, 1,2-dime-thyl-n-propylen-, 1,3-dimethyl-n-propylen-, 1,1-35 dimethyl-n-butylen-, 2,2-dimethyl-n-butylen-, 3,3-dimethyl-n-butylen-, 4,4-dimethyl-n-butylen-, 5no, N-bromobenzoyl sulfoxymino, N-methylbenzoyl sulfoxymino, N-ethylbenzoyl sulfoxymino, N-isopropylbenzoyl sulfoxymino, N-tert-butyl benzoyl sulfoxymino, N-difluorobenzoyl sulfoxymino , N-dichlorobenzoyl sulfoxymino, N-dimethylbenzoyl sulfoxymino, N-trimethylbenzoyl sulfoxymino, N-naphthoyl sulfoxymino, N-pyridinoyl sulfoxymino, N-thenoyl sulfoxymino, N-acetoxy -benzoyl-sulfoxymino-, N-hydroxy-sulfoxymino-, N-methanesulfonyl-sulfoxymino-, N-ethanesulfonylsulfoxymino-, N-phenylsulfonylsulfonylsulfoxymino-, N-methylphenylsulfonylsulfoxymino-, N-fluorophenylsulfonylsulfonylsulfonyl , N-chlorophenylsulfonylsulfoxymino, N-bromophenylsulfonylsulfoxymino, N-pentamethylphenylsulfoxymino, N-naphthylsulfonylsulfoxymino, N-methoxycarbonylsulfoxymino, N-ethoxycarbonylsulfoxymino -sulfoxymino, N-isopropoxy-carbonyl-sulfoxymino, N-benzyloxycarbonyl-sulfoxy-amino, N-aminocarbonyl-sulfoxymino, N-methylaminocarbonyl-sulfoxymino or N-dimethyl minocarbonylsulfoxymino group, for D an ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, 1-methylethylene, 2-methylethylene, 1- methyl-n-propylene, 2-methyl-n-propylene, 3-methyl-n-propylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n -butylene, 4-methyl-n-butylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene , 5-methyl-n-pentylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2-dimethylethylene, 1,1-dimethyl-n-propylene, 2, 2-dimethyl-n-propylene, 3,3-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 1,3-dimethyl-n-propylene, 1,1-35 dimethyl -n-butylene, 2,2-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 4,4-dimethyl-n-butylene,
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1,2-dimethyl-n-butylen-, 1,3-dimethyl-n-butylen-, 1,4-dimethyl-n-butylen-, 2,3-dimethyl-n-butylen-, 1-ethyl-ethylen-, 2-ethyl-ethylen-, 1-ethyl-n-propylen-, 2-ethyl-n-propylen-, 3-ethyl-n-propy-5 len-, 1-ethyl-n-butylen-, 2-ethyl-n-butylen-, 3-ethyl-n-butylen-, 4-ethyl-n-butylen-, 1-methyl--2-ethyl-ethylen-, l-methyl-2-ethyl-n-propylen-, l-methyl-3-ethyl-n-propylen-, l-methyl-2-propyl-ethylen-, 1-propyl-ethylen-, 1-butyl-ethylen- el-10 ler 1-propyl-n-propylengruppe, for Ri en methyl-, ethyl-, n-propyl-, isopropyl-, n-bu-tyl-, 1-methyl-propyl-, 2-methyl-propyl-, tert. butyl-, n-pentyl-, 1-methyl-n-butyl-, 2-methyl-n-butyl-, 3-methyl-n-butyl-, 1-ethyl-n-propyl-, 15 tert.pentyl-, n-hexyl-, n-heptyl-, n-octyl-, ben zyl-, 1-phenylethyl-, 2phenyl-ethyl-, 1-phenyl-propyl-, 3-phenylpropyl-, fluorbenzyl-, chlorben-zyl-, brombenzyl-, methylbenzyl-, isopropylben-zyl-, methoxybenzyl-, ethoxybenzyl, cyclopropyl-, 20 cyclobutyl-, cyclo-pentyl-, cyclohexyl-, cyclo- heptyl-, phenyl-, fluorphenyl-, chlorphenyl-, bromphenyl-, methyl-phenyl-, isopropylphenyl-, tert.butylphenyl-, hydroxypheny1-, methoxyphe-nyl-, ethoxyphenyl-, n-propoxyphenyl-, formylami-25 nophenvl-, acetylaminophenyl-, propionylaminophe- nyl-, cyclohexylphenyl-, biphenylyl-, difluorphe-nyl-, dichlorphenyl-, dibromphenyl-, dimethoxy-phenyl-, methoxy-chlorphenyl-, methoxy-bromphe-nyl-, dimethylphenyl-, methyl-ethylphenyl-, di-30 ethylphenyl-, methyl-tert,butylphenyl-, methyl- chlorphenyl-, methyl-bromphenyl-, tert.butyl-brom-phenyl-, trimethylphenyl-, dichlor-aminophe-nyl-, dibrom-aminophenyl-, dimethy1-aminophenyl-, dichlor-hydroxyphenyl-, dibrom-hydroxypheny1-, 35 dimethyl-hydroxyphenyl-, di-tert.butyl-hydroxy- phenyl-, trimethoxyphenyl-, pyridyl-, pyridyl-N- 61,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 1,4-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 1-ethylethylene , 2-ethyl-ethylene, 1-ethyl-n-propylene, 2-ethyl-n-propylene, 3-ethyl-n-propylene, 1-ethyl-n-butylene, 2-ethyl -n-butylene-, 3-ethyl-n-butylene-, 4-ethyl-n-butylene-, 1-methyl-2-ethyl-ethylene-, 1-methyl-2-ethyl-n-propylene-, 1 -methyl-3-ethyl-n-propylene, 1-methyl-2-propyl-ethylene, 1-propyl-ethylene, 1-butyl-ethylene, or 1-propyl-n-propylene group, for R 1 and methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-propyl, 2-methyl-propyl, tert. butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-ethyl-n-propyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, 1-phenylethyl, 2-phenyl-ethyl, 1-phenyl-propyl, 3-phenylpropyl, fluorobenzyl, chlorobenzyl, bromobenzyl -, methylbenzyl, isopropylbenzyl, methoxybenzyl, ethoxybenzyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, fluorophenyl, chlorophenyl, bromophenyl, methylphenyl -, isopropylphenyl, tert.butylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, n-propoxyphenyl, formylaminophenyl, acetylaminophenyl, propionylaminophenyl, cyclohexylphenyl, biphenyl, biphenyl , dichlorophenyl, dibromophenyl, dimethoxyphenyl, methoxy-chlorophenyl, methoxy-bromophenyl, dimethylphenyl, methylethylphenyl, diethylphenyl, methyl tert, butylphenyl, methyl chlorophenyl, methyl bromophenyl, tert.butyl bromo-phenyl, trimethylphenyl, dichloro-aminophenyl, dibromo-aminophenyl, dimeth γ1-aminophenyl, dichloro-hydroxyphenyl, dibromo-hydroxyphenyl, dimethyl-hydroxyphenyl, di-tert-butyl-hydroxyphenyl, trimethoxyphenyl, pyridyl, pyridyl-N-6
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oxid-, methyl-pyridyl-, ethyl-pyridyl-, dimethyl-pyridyl-, pyrimidinyl-, methyl-pyrimidinyl-, ethyl-pyrimidinyl-, propyl-pyrimidinyl-, dime-thyl-pyrimidinyl-, diethyl-pyrimidinyl-, pyrazi-5 nyl-, pyridazinyl-, pyrazolyl-, imidazolyl-, triazolyl-, indolyl-, indazolyl-, chinolyl-, iso-chinolyl-, chinazolinyl-, benziraidazolyl-eller benzthiazolylgruppe, for R2 og R3, der lean være ens eller forskellige, i 10 hvert tilfælde et hydrogenatom, en methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, 1-rae-thyl-n-propyl-, 2-methyl-n-propyl-, tert.-butyl-, n-pentyl-, 1-methyl-n-butyl-, 2-me thyl-n-butyl-, 3-methyl-n-butyl-, 1-ethyl-n-propyl-, tert.pen-15 tyl-, n-hexyl-, phenyl-, cyclopropyl-, cyclobu- tyl-, cyclopentyl-, cyclohexyl- eller cyclohep-tylgruppe, for R4 et hydrogenatom, en methyl-, ethyl-, n-propyl-eller isopropylgruppe, 20 for R5 et hydrogen-, fluor-, chlor-, brom- eller iod- atom, en nitro-, methyl-, ethyl-, n-propyl-eller isopropylgruppe og for Rq et hydrogen-, fluor-, chlor- eller bromatom, en methyl-, ethyl-, n-propyl- eller isopropyl-gruppe 25 i betragtning.oxide, methyl pyridyl, ethyl pyridyl, dimethyl pyridyl, pyrimidinyl, methyl pyrimidinyl, ethyl pyrimidinyl, propyl pyrimidinyl, dimethyl pyrimidinyl, diethyl pyrimidinyl, pyrazide 5, nyl, pyridazinyl, pyrazolyl, imidazolyl, triazolyl, indolyl, indazolyl, quinolyl, isoquinolyl, quinazolinyl, benziraidazolyl or benzthiazolyl group, for R 2 and R 3, which are the same or different, in each case, a hydrogen atom, a methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-n-propyl, 2-methyl-n-propyl, tertiary compound, butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-ethyl-n-propyl, tert-pen-15 tyl, n-hexyl, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclohepthyl group, for R 4 a hydrogen atom, a methyl, ethyl, n-propyl or isopropyl group, for R5 is a hydrogen, fluoro, chloro, bromo or iodo atom, a nitro, methyl, ethyl, n-propyl or isopropyl group and for Rq a hydrogen, fluoro, chloro or bromine atom, a methyl, ethyl, n-propyl or isopropyl group 25 under consideration.
Foretrukne forbindelser fremstillet ifølge opfindelsen er sådanne, hvori A er et svovlatom, en SO-, S02~# ,R-N=S- eller R-N-=S0-gruppe, hvorved 30 R er et hydrogenatom, en eventuelt med en methylgrup-pe substitueret benzoyl- eller phenylsulfonylgrup-pe, en acetyl- eller propionylgruppe, D er en ligekædet alkylengruppe med 2 til 6 carbonato-mer, 35 Ri er en alkylgruppe med 1 til 8 carbonatomer, en cyclohexyl-, benzyl-, pyridyl-, pyridyl-N-oxid-, 2-benz-thiazolyl- eller l,2,4-triazol-3-ylgruppe, en eventuelt med en eller to methylgrupper substitueret 2- 7Preferred compounds of the invention are those in which A is a sulfur atom, an SO, SO 2 -, RN = S or RN- = SO group, wherein R is a hydrogen atom, optionally substituted with a methyl group of benzoyl. - or phenylsulfonyl group, an acetyl or propionyl group, D is a straight chain alkylene group of 2 to 6 carbon atoms, R 1 is an alkyl group of 1 to 8 carbon atoms, a cyclohexyl, benzyl, pyridyl, pyridyl N oxide, 2-benz-thiazolyl or 1,2,4-triazol-3-yl group, optionally substituted with one or two methyl groups 2-7
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pyrimidinylgruppe, en eventuelt med en alkylgruppe med 1 til 4 carbonatomer, en med en hydroxy-, methoxy-, cyc-lohexyl-, phenyl- eller acetylaminogruppe, et fluor-, chlor- eller bromatom substitueret phenylgruppe, en 5 med chlor- eller bromatomer, methyl- eller methoxy-grupper disubstitueret phenylgruppe, hvori substitu-enterne i phenylkernen kan være ens eller forskellige, eller en med to alkylgrupper med hver 1 til 4 carbonatomer, to chlor- eller bromatomer substitueret 10 aminophenyl- eller hydroxyphenylgruppe, R2 og R3, der kan være ens eller forskellige, er hydrogenatomer, alkylgrupper med 1 til 6 carbonatomer, phenyl- eller cyclohexylgrupper, R4 er et hydrogenatom eller en methylgruppe, 15 R5 er et hydrogen-, fluor-, chlor- eller bromatom, en nitro-, methyl- eller ethylgruppe, og R5 er et hydrogen-, chlor- eller bromatom, en methyl-eller ethylgruppe, især dog de forbindelser, hvori gruppen -O-D-A-Ri står i 6-stilling.pyrimidinyl group, one optionally having an alkyl group having 1 to 4 carbon atoms, one having a hydroxy, methoxy, cyclohexyl, phenyl or acetylamino group, a fluoro, chloro or bromine atom substituted phenyl group, a 5 with chloro or bromine atom , methyl or methoxy groups disubstituted phenyl group, wherein the substituents in the phenyl nucleus may be the same or different, or one having two alkyl groups each having 1 to 4 carbon atoms, two chloro or bromine atoms substituted 10 aminophenyl or hydroxyphenyl group, R 2 and R 3, which may be the same or different are hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, phenyl or cyclohexyl groups, R 4 is a hydrogen atom or a methyl group, R 5 is a hydrogen, fluoro, chloro or bromine atom, a nitro, methyl - or ethyl group, and R 5 is a hydrogen, chlorine or bromine atom, a methyl or ethyl group, especially however the compounds in which the -ODA-R 1 group is in the 6-position.
20 Særligt foretrukne forbindelser fremstillet ifølge opfindelsen er forbindelserne med den almene formel la 20 1 I.Particularly preferred compounds of the invention are the compounds of the general formula Ia 20 1 I.
R6 b 30 hvori A er en SO—, SO2*·» H—N=SO—, CH3CO—N=SO— og CH3—CgH^— S02~N=S0-gruppe, D er en n-butylengruppe, 8R6 b 30 wherein A is a SO-, SO2 * · H-N = SO-, CH3CO-N = SO- and CH3-CgH2 - SO2 ~ N = SO group, D is an n-butylene group, 8
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Ri er en eventuelt med et fluor-, chlor- eller bromatom, en methyl-, hydroxy-, methoxy-, cyclohexyl-, phenyl-eller acetaminogruppe substitueret phenyl-gruppe, en med chlor- eller bromatomer, methyl- eller methoxy-5 grupper disubstitueret phenylgruppe, hvori substitu-enterne i phenylkernen kan være ens eller forskellige, en 4-amino-3,5-dibrom-phenyl-, en 3,5-di-tert.buty 1-4-hydroxy-phenyl- eller pyridylgruppe, R2 og R3,der kan være ens eller forskellige, hver er et 1 g hydrogenatom eller en methylgruppe, R5 er et hydrogen-, chlor- eller bromatom, en nitro-eller methylgruppe, ogR 1 is an optionally substituted phenyl group with a fluorine, chlorine or bromine atom, a methyl, hydroxy, methoxy, cyclohexyl, phenyl or acetamino group, a chloro or bromine atom, methyl or methoxy groups disubstituted phenyl group wherein the substituents in the phenyl nucleus may be the same or different, a 4-amino-3,5-dibromo-phenyl, a 3,5-di-tert-butyl 1-4-hydroxy-phenyl or pyridyl group, R 2 and R 3, which may be the same or different, are each a 1 g hydrogen atom or a methyl group, R 5 is a hydrogen, chlorine or bromine atom, a nitro or methyl group, and
Rg er et hydrogen-, chlor- eller bromatom eller en methylgruppe .Rg is a hydrogen, chlorine or bromine atom or a methyl group.
15 Ifølge opfindelsen fremstilles de hidtil ukendte forbindelser som nævnt ved:According to the invention, the novel compounds are prepared as mentioned by:
a) Omsætning af en hydroxy forbindelse med den almene formel IIa) Reaction of a hydroxy compound of general formula II
- vk "t 1 >0- vk "t 1> 0
Kc 6 R/ 25 4 hvori R2 til Rg er som defineret tidligere, eller salte deraf med uorganiske eller tertiære organiske baser,Kc 6 R / 25 4 wherein R2 to Rg are as previously defined, or salts thereof with inorganic or tertiary organic bases,
2Q med en forbindelse med den almene formel III2Q having a compound of general formula III
Z - D - A - Ri IIIZ - D - A - Ri III
99
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hvori A, D og Ri er som defineret tidligere, og Z er en nu-cleofil fraspaltelig gruppe såsom et halogenatom eller en sulfonsyreestergruppe, f.eks. et chlor-, brom-5 eller iodatom, en p-toluensulfonyloxy- eller methan-sulfonyloxygruppe.wherein A, D and R 1 are as previously defined and Z is a nucleophilic leaving group such as a halogen atom or a sulfonic acid ester group, e.g. a chlorine, bromine or iodine atom, a p-toluenesulfonyloxy or methanesulfonyloxy group.
Omsætningen gennemføres hensigtsmæssigt i et egnet opløsningsmiddel eller en opløsningsmiddelblanding såsom methanol, ethanol, dioxan, tetrahydrofu-10 ran, chloroform eller toluen, dog fortrinsvis i et vandfrit aprot opløsningsmiddel såsom acetone, dime-thylformamid eller dimethylsulfoxid, eventuelt i nærværelse af en alkalibase eller et alkoholat såsom na-triumcarbonat, kaliumcarbonyl, natriumhydroxid eller 15 natriumethylat ved temperaturer mellem 0°C og det anvendte opløsningsmiddels kogepunkt, f.eks. ved temperaturer mellem 0 og 100°C, dog fortrinsvis ved temperaturer mellem 10 og 80°C. Omsætningen kan dog også gennemføres uden opløsningsmiddel.The reaction is conveniently carried out in a suitable solvent or solvent mixture such as methanol, ethanol, dioxane, tetrahydrofuran, chloroform or toluene, but preferably in an anhydrous aprotic solvent such as acetone, dimethylformamide or dimethylsulfoxide, optionally in the presence of an alkali or an alkali or an alkali alcoholate such as sodium carbonate, potassium carbonyl, sodium hydroxide or sodium ethylate at temperatures between 0 ° C and the boiling point of the solvent used, e.g. at temperatures between 0 and 100 ° C, but preferably at temperatures between 10 and 80 ° C. However, the reaction can also be carried out without solvent.
20 b) Til fremstilling af forbindelser med den almene formel I, hvori A er en SO-, S02~ eller R-N=SO-gruppe:B) For the preparation of compounds of the general formula I wherein A is a SO, SO 2 or R-N = SO group:
Oxidation af en forbindelse med den almene formel IVOxidation of a compound of general formula IV
25 R- H, R, 30 Rc R, O “ hvori25 R-H, R, 30 Rc R, O 'wherein
Ri til R5 og D har de tidligere definitioner, og A' er et svovlatom, en SO- eller R-N=S-gruppe, hvori R 35 er som defineret tidligere.R 1 to R 5 and D have the previous definitions, and A 1 is a sulfur atom, an SO or R-N = S group, wherein R 35 is as previously defined.
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Oxidationen gennemføres fortrinsvis i et opløsningsmiddel eller en opløsningsmiddelblanding, f.eks. i vand, vand/pyridin, ethanol, methanol, acetone, iseddikesyre, myresyre, fortyndet svovlsyre eller tri-5 fluoreddikesyre, alt efter det anvendte oxidations middel hensigtsmæssigt ved temperaturer mellem -80 og 100°C.The oxidation is preferably carried out in a solvent or solvent mixture, e.g. in water, water / pyridine, ethanol, methanol, acetone, glacial acetic acid, formic acid, dilute sulfuric acid or trifluoroacetic acid, depending on the oxidizing agent used, suitably at temperatures between -80 and 100 ° C.
Til fremstilling af forbindelser med den almene formel I, hvori R er en SO- eller R-N=SO-gruppe, 10 gennemføres oxidationen hensigtsmæssigt med et ækvivalent af det anvendte oxidationsmiddel, f.eks. med hydrogenperoxid i iseddikesyre eller myresyre ved 0 til 20°C eller i acetone ved 0 til 60°C, med en persyre såsom permyresyre eller m-chlor-perbenzoe-syre i 15 iseddikesyre eller trifluoreddikesyre ved 0 til 20°C, med natriummetaperiodat i vandig methanol eller ethanol ved 15 til 25°C, med N-brom-succinimid i ethanol ved 10 til 50°C, med tert.butyl-hypochlorit i methanol ved -80 til -30°C, med iodbenzendichlorid i van-20 dig pyridin ved 0 til 20°C, med chromsyre i iseddikesyre eller i acetone ved 0 til 20°C og med sulfuryl-chlorid i methylenchlorid ved -70°C, idet det herved opnåede thioether-chlor-kompleks hensigtsmæssigt hydrolyseres med vandig ethanol.For the preparation of compounds of general formula I wherein R is an SO or R-N = SO group, the oxidation is conveniently carried out with an equivalent of the oxidizing agent used, e.g. with hydrogen peroxide in glacial acetic acid or formic acid at 0 to 20 ° C or in acetone at 0 to 60 ° C, with a peracid such as permyric acid or m-chloro-perbenzoic acid in glacial acetic acid or trifluoroacetic acid at 0 to 20 ° C, with sodium metaperiodate in aqueous methanol or ethanol at 15 to 25 ° C, with N-bromo-succinimide in ethanol at 10 to 50 ° C, with tert.butyl hypochlorite in methanol at -80 to -30 ° C, with iodobenzene dichloride in water pyridine at 0 to 20 ° C, with chromic acid in glacial acetic acid or in acetone at 0 to 20 ° C, and with sulfuryl chloride in methylene chloride at -70 ° C, the resulting thioether-chloro complex being suitably hydrolyzed with aqueous ethanol.
25 Til fremstilling af forbindelser med den almene formel I, hvori A er en S02~gruppe, gennemføres oxidationen hensigtsmæssigt med et eller to eller flere ækvivalenter af det anvendte oxidationsmiddel, f.eks. med hydrogenperoxid i iseddikesyre eller i myresyre 30 ved 20 til 100°C eller i acetone ved 0 til 60°C, med en persyre såsom permyresyre eller m-chlorperbenzoe-syre i iseddikesyre, trifluoreddikesyre eller chloro- 11To prepare compounds of the general formula I wherein A is a SO 2 group, the oxidation is conveniently carried out with one or two or more equivalents of the oxidizing agent used, e.g. with hydrogen peroxide in glacial acetic acid or in formic acid 30 at 20 to 100 ° C or in acetone at 0 to 60 ° C, with a peracid such as permyric acid or m-chloroperbenzoic acid in glacial acetic acid, trifluoroacetic acid or chloro-11
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form ved temperaturer mellem 0 og 50°C, med salpetersyre i iseddikesyre ved 0 til 20°C/ med chromsyre eller kaliumpermanganat i iseddikesyre, vand/svovlsyre eller i acetone ved 0 til 20°C. Er A følgelig i en 5 forbindelse med den ovenstående almene formel IV et svovlatom, gennemføres omsætningen fortrinsvis med to eller flere ækvivalenter af det pågældende oxidationsmiddel og helt tilsvarende med mindst et ækvivalent, såfremt A er en SO-gruppe.form at temperatures between 0 and 50 ° C, with nitric acid in glacial acetic acid at 0 to 20 ° C / with chromic acid or potassium permanganate in glacial acetic acid, water / sulfuric acid or in acetone at 0 to 20 ° C. Accordingly, if A is in a compound of the above general formula IV a sulfur atom, the reaction is preferably carried out with two or more equivalents of the oxidizing agent in question and quite similarly with at least one equivalent if A is an SO group.
10 c) Til fremstilling af forbindelser med den almene formel I, hvori A er et svovlatom eller en S02~gruppe: Omsættes en forbindelse med den almene formel VC) For the preparation of compounds of the general formula I wherein A is a sulfur atom or a SO 2 group: a compound of the general formula V is reacted
r, r2 r3 20 4 hvorir, r2 r3 20 4 wherein
D og R2 til Rg er defineret som tidligere, og X er en nucleofil fraspaltelig gruppe såsom et halogenatom 25 eller en sulfonsyreesterrest, f.eks. et chlor-, bromeller iodatom, en p-toluensulfonyloxy- eller methan-sulfonyloxygruppe, med en forbindelse med den almene formel VID and R 2 to R 9 are defined as before and X is a nucleophilic leaving group such as a halogen atom or a sulfonic acid ester residue, e.g. a chlorine, bromine or iodine atom, a p-toluenesulfonyloxy or methanesulfonyloxy group, having a compound of the general formula VI
Y - Ri VIY - Ri VI
30 hvori R er defineret som tidligere, og Y er en MeS02~ gruppe, hvorved Me er et alkali- eller jordalkali/2-metalatom, såsom natrium-, kalium- eller calcium/2- atom eller en mercaptogruppe.Wherein R is as previously defined and Y is a MeSO 2 group wherein Me is an alkali or alkaline earth / 2 metal atom such as sodium, potassium or calcium / 2 atom or a mercapto group.
Omsætningen gennemføres hensigtsmæssigt i et eg-35 net opløsningsmiddel eller opløsningsmiddelblanding, såsom dioxan, tetrahydrofuran, chloroform eller tolu- 12The reaction is conveniently carried out in a suitable solvent or solvent mixture such as dioxane, tetrahydrofuran, chloroform or toluene.
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en, dog fortrinsvis i et vandfrit aprot opløsningsmiddel såsom acetone, dimethylformamid eller dime-thylsulfsoxid, eventuelt i nærværelse af en alkalibase, såsom natriumcarbonat, kaliumcarbonat eller na-5 triumhydroxid ved temperaturer mellem 0°C og det an vendte opløsningsmiddels kogetemperatur, f.eks. ved temperaturer mellem 0 og 100°C, dog fortrinsvis ved temperaturer mellem 10 og 50°C. Omsætningen kan dog også gennemføres uden opløsningsmiddel.one, however preferably in an anhydrous aprotic solvent such as acetone, dimethylformamide or dimethyl sulfoxide, optionally in the presence of an alkali base such as sodium carbonate, potassium carbonate or sodium hydroxide at temperatures between 0 ° C and the boiling temperature of the solvent used, e.g. . at temperatures between 0 and 100 ° C, but preferably at temperatures between 10 and 50 ° C. However, the reaction can also be carried out without solvent.
10 d) Til fremstilling af forbindelser med den almene formel I, hvori A er en H-N=SO-gruppe:D) For the preparation of compounds of general formula I wherein A is an H-N = SO group:
Omsættes et sulfoxid med den almene formel VIIA sulfoxide of the general formula VII is reacted
R1 - SO - D - 0--j |_ 0 vil ; ^ *· % 20 hvori D og Ri til Rg er defineret som tidligere, med eventuelt i reaktionsblandingen dannet nitrogenhydrogen-syre.R1 - SO - D - 0 - j | _ 0 will; % 20 wherein D and R 1 to R 9 are defined as before, with optionally formed nitrogen hydrogen acid in the reaction mixture.
Omsætningen gennemføres hensigtsmæssigt i et op- 25 løsningsmiddel eller en opløsningsmiddelblanding, så som methylenchlorid, dimethylformamid eller tetrahy-drofuran ved temperaturer mellem 0 og 40°C, fortrinsvis ved temperaturer mellem 10 og 35°C. Særligt fordelagtigt gennemføres omsætningen med et alkaliazid, 30 f.eks. natriumazid og polyphosphorsyre som opløs ningsmiddel.The reaction is conveniently carried out in a solvent or solvent mixture such as methylene chloride, dimethylformamide or tetrahydrofuran at temperatures between 0 and 40 ° C, preferably at temperatures between 10 and 35 ° C. Particularly advantageously, the reaction is carried out with an alkali metal, e.g. sodium azide and polyphosphoric acid as solvent.
e) Til fremstilling af forbindelser med den almene formel I, hvori A er en H-N=SO-gruppe:e) For the preparation of compounds of general formula I wherein A is an H-N = SO group:
Omsættes et sulfoxid med den almene formel VIIA sulfoxide of the general formula VII is reacted
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R ftp ft-,R ftp ft-,
Vy^ R., - SO - D - C--I °Vy ^ R., - SO - D - C - I °
5 ^Λκ^0 VII5 ^ Λκ ^ 0 VII
Rfi 6 R4 hvoriRfi 6 R4 wherein
10 D og Ri til Rg er defineret som tidligere, med en forbindelse med den almene formel VIIID and R 1 to R 9 are defined as before, with a compound of the general formula VIII
H2N - 0 - X - r VIIIH2N - 0 - X - r VIII
hvori X er en carbonyl- eller sulfonylgruppe, og R7 er en i 15 o-stilling disubstitueret arylgruppe såsom en 2,4,6-trimethylphenyl- eller 2,4,6-triisopropylphe-nylgruppe .wherein X is a carbonyl or sulfonyl group and R 7 is an aryl substituted aryl group such as a 2,4,6-trimethylphenyl or 2,4,6-triisopropylphenyl group.
Omsætningen gennemføres hensigtsmæssigt i et opløsningsmiddel eller en opløsningsmiddelblanding så-20 som methylenchlorid, chloroform, dimethylformamid, tetrahydrofuran eller dioxan ved temperaturer mellem 0 og 50°C, dog fortrinsvis ved temperaturer mellem 5 og 40°C, og eventuelt i nærværelse af en katalytisk mængde syre, såsom p-toluensulfonsyre. Omsætningen 25 gennemføres dog særligt fordelagtig på den måde, at en forbindelse med den almene formel VIII anvendes uden dens forudgående isolering eller fremstilles i reaktionsblandingen.The reaction is conveniently carried out in a solvent or solvent mixture such as methylene chloride, chloroform, dimethylformamide, tetrahydrofuran or dioxane at temperatures between 0 and 50 ° C, but preferably at temperatures between 5 and 40 ° C, and optionally in the presence of a catalytic amount. acid such as p-toluenesulfonic acid. However, reaction 25 is carried out particularly advantageously in that a compound of general formula VIII is used without its prior isolation or prepared in the reaction mixture.
f) Til fremstilling af en forbindelse med den almene 30 formel I, hvori R ikke er et hydrogenatom:f) For the preparation of a compound of general formula I wherein R is not a hydrogen atom:
Acyleres en forbindelse med den almene formel IXA compound of the general formula IX is acylated
R, R,R, R,
VsXVSX
« R.-A”-D-0-- I"R.-A" -D-0-- I
35 1 R6 r4 1435 1 R6 r4 14
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hvori D og Ri til Rg er defineret som tidligere, og A" er en H-N=S- eller H-N=S0-gruppe.wherein D and R 1 to R 9 are defined as before and A "is an H-N = S or H-N = SO group.
Omsætningen gennemføres hensigtsmæssigt i et op-5 løsningsmiddel eller en opløsningsmiddelblanding, såsom vand, methylenchlorid, chloroform, ether, tetra-hydrofuran, dioxan eller dimethylformamid med et passende acyleringsmiddel, f.eks. med en syre i nærværelse af et middel, der aktiverer syren eller er 10 vandsugende såsom thionylchlorid, med dets anhydri-der, såsom eddikesyreethylhyandrid, med dets estere, såsom p-toluensulfonsyreethylester eller kulsyredi-ethylester, med dets halogenider såsom acetylchlorid, chlormyresyreethylester eller p-toluensulfonsyre-15 chlorid, eller med et passende isocyanat, hvorved dette eventuelt også kan virke som opløsningsmiddel, eventuelt i nærværelse af en uorganisk eller tertiær, organisk base, såsom natriumhydroxid, kaliumcarbonat, triethylamin eller pyridin, hvorved de sidstnævnte 20 også samtidig kan virke som opløsningsmiddel ved tem peraturer mellem -25 og 100°C, dog fortrinsvis ved temperaturer mellem -10 og 80°C.The reaction is conveniently carried out in a solvent or solvent mixture such as water, methylene chloride, chloroform, ether, tetrahydrofuran, dioxane or dimethylformamide with a suitable acylating agent, e.g. with an acid in the presence of an agent which activates the acid or is water-sucking such as thionyl chloride, with its anhydrides such as acetic acid ethyl hybride, with its esters such as p-toluenesulfonic acid ethyl ester or carbonic acid ethyl ester, with its halides such as acetyl chloride, chloroacetic acid or -toluenesulfonic acid chloride, or with an appropriate isocyanate, whereby it may also act as a solvent, optionally in the presence of an inorganic or tertiary organic base such as sodium hydroxide, potassium carbonate, triethylamine or pyridine, whereby the latter may also act simultaneously. as a solvent at temperatures between -25 and 100 ° C, but preferably at temperatures between -10 and 80 ° C.
g) Til fremstilling af en forbindelse med den almene formel I, hvori A er en R-N=S-gruppe:g) For the preparation of a compound of general formula I wherein A is an R-N = S group:
25 Omsættes en thioether med den almene formel XA thioether of the general formula X is reacted
D R RD R R
R.-S-D-C-- IR.-S-D-C-- I
30 ^ 0 r6 r, 35 hvori30 ^ 0 r6 r, 35 wherein
Ri til Rg og D er defineret som tidligere med et halogenamid med den almene formel XIR 1 to R 9 and D are as previously defined with a halogenamide of general formula XI
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HalHall
R1 - NR1 - N
^ H XI^ H XI
5 hvori R*, bortset fra et hydrogenatom, har de for R tidligere nævnte betydninger, og Hal er et chlor- eller bromatom eller med dettes alkalisalt og eventuelt efterfølgende hydrolyse.5 wherein R *, other than a hydrogen atom, has the meanings previously mentioned for R and Hal is a chlorine or bromine atom or with its alkali salt and optionally subsequent hydrolysis.
10 Omsætningen gennemføres fortrinsvis med et alka lisalt af en forbindelse med den almene formel XI, f.eks. natriumsaltet, eventuelt i nærværelse af en uorganisk base, såsom en alkalibase i et opløsningsmiddel eller en opløsningsmiddelblanding, såsom me- 15 thanol, methanol/vand eller ethanol, hensigtsmæssigt ved temperaturer mellem 0 og 80°C, dog fortrinsvis ved temperaturer mellem 5 og 50°c.The reaction is preferably carried out with an alkaline salt of a compound of the general formula XI, e.g. the sodium salt, optionally in the presence of an inorganic base such as an alkali base in a solvent or a solvent mixture such as methanol, methanol / water or ethanol, conveniently at temperatures between 0 and 80 ° C, but preferably at temperatures between 5 and 50 ° C.
Den eventuelt efterfølgende hydrolyse gennemføres i nærværelse af en syre eller base, dog fortrinsvis i 20 nærværelse af en base såsom natriumhydroxid, i et opløsningsmiddel eller en opløsningsmiddelblanding såsom vand, methanol, methanol/vand eller tetrahydro-furan/vand ved temperaturer op til det anvendte opløsningsmiddels kogetemperatur.The optionally subsequent hydrolysis is carried out in the presence of an acid or base, but preferably in the presence of a base such as sodium hydroxide, in a solvent or solvent mixture such as water, methanol, methanol / water or tetrahydrofuran / water at temperatures up to the used temperature. solvent boiling temperature.
25 h) Til fremstilling af en forbindelse med den almene formel I, hvori A er en H-N=S- eller H-N=SO-gruppe: Fraspaltes en acylrest hydrolytisk fra en forbindelse med den almene formel XIIH) To prepare a compound of general formula I wherein A is an H-N = S or H-N = SO group: an acyl residue is hydrolytically cleaved from a compound of general formula XII
R_ RR_ R
R “A* 1 —D—0— : XIIR “A * 1 — D — 0—: XII
><A.> °> <A.> °
RR
35 D *4 1635 D * 4 16
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hvori D og Ri til Rg er defineret som tidligere, og A’" er en med en hydrolytisk fraspaltelig acylrest substitueret H-N=S- eller H-N=S0-gruppe.wherein D and R 1 to R 9 are as previously defined and A 1 is a H-N = S or H-N = SO group substituted with a hydrolytically cleavable acyl residue.
5 Som acylrest kan f.eks. en carboxylsyre eller et kulsyrederivat komme i betragtning, såsom en acetyl-, propionyl-, butanoyl-, benzoyl-, pinanoyl-, nicoti-noyl-, ethoxycarbonyl-, aminocarbonyl- eller dime-thylaminocarbonylgruppe.As an acyl residue, e.g. a carboxylic acid or a carbonic acid derivative is contemplated such as an acetyl, propionyl, butanoyl, benzoyl, pinanoyl, nicotinoyl, ethoxycarbonyl, aminocarbonyl or dimethylaminocarbonyl group.
10 Omsætningen gennemføres i nærværelse af en syre eller base, f.eks. i nærværelse af saltsyre, svovlsyre, natronlud, kalilud eller kaliumcarbonat i et opløsningsmiddel eller en opløsningsmiddelblanding såsom vand, methanol, vand/methanol, vand/ethanol el- 15 ler vand/tetrahydrofuran ved temperaturer op til det anvendte opløsningsmiddels kogetemperatur, f.eks. ved temperaturer mellem 50 og 90°C.The reaction is carried out in the presence of an acid or base, e.g. in the presence of hydrochloric acid, sulfuric acid, sodium hydroxide, potassium liquor or potassium carbonate in a solvent or solvent mixture such as water, methanol, water / methanol, water / ethanol or water / tetrahydrofuran at temperatures up to the boiling temperature of the solvent used, e.g. at temperatures between 50 and 90 ° C.
i) Til fremstilling af en forbindelse med den almene formel I, hvori R ikke er et hydrogenatoms 20 Omsættes en forbindelse med den almene formeli) For the preparation of a compound of general formula I wherein R is not a hydrogen atom A compound of the general formula is reacted
XIIIXIII
Re / 5 >fy "ohRe / 5> fy "oh
25 , XIII25, XIII
R -Å""-D-0 -- HR -Å "" - D-0 - H
*6 4 30 hvori D og Ri til Rg er defineret som tidligere, og A"" er et svovlatom, en SO-, S02~, R'-N=S- eller R'-N=S0-gruppe, hvorved R', bortset fra et hydrogenatom, har de for R tidligere nævnte betydninger, med et kulsy-Wherein D and R 1 to R 9 are as previously defined and A "" is a sulfur atom, an SO, SO 2, R'-N = S or R'-N = SO group, where R ' except for a hydrogen atom, have the meanings for R previously mentioned, with a carbon dioxide.
35 rederivat med den almene formel XIV35 derivatives of general formula XIV
X - CO - X XIVX - CO - X XIV
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hvori X, der kan være ens eller forskellige, i hvert tilfælde er en nucleofil afgangsgruppe såsom et chlor-atom, en methoxy-, ethoxy-, benzyloxyl- eller imida-5 zolylgruppe.wherein X, which may be the same or different, is in each case a nucleophilic leaving group such as a chlorine atom, a methoxy, ethoxy, benzyloxyl or imidazolyl group.
Omsætningen gennemføres hensigtsmæssigt i et inert opløsningsmiddel såsom ether, chloroform, dioxan, toluen’ eller tetrahydrofuran/toluen ved temperaturer mellem 0 og 80°C, dog fortrinsvis ved 10 stuetemperatur.The reaction is conveniently carried out in an inert solvent such as ether, chloroform, dioxane, toluene or tetrahydrofuran / toluene at temperatures between 0 and 80 ° C, but preferably at room temperature.
Opnås der ved opfindelsen en forbindelse med den almene formel I, hvori R4 er et hydrogenatom, kan dette ved hjælp af alkylering overføres i en tilsvarende forbindelse med den almene formel I, hvori R4 15 er en alkylgruppe med 1 til 3 carbonatomer.If the invention provides a compound of general formula I wherein R 4 is a hydrogen atom, this can be carried out by alkylation in a corresponding compound of general formula I wherein R 4 is an alkyl group having 1 to 3 carbon atoms.
Den efterfølgende alkylering gennemføres hensigtsmæssigt med et alkylhalogenid såsom methyliodid eller propylbromid eller en sulfonsyreester, såsom dimethylsulfat, fortrinsvis i nærværelse af en base 20 såsom natriumhydroxid eller pyridin, eventuelt i nærværelse af en reaktionsaccelerator, såsom tetra-butylammonium-hydrogensulfat og fortrinsvis i et opløsningsmiddel såsom methanol, ethanol, vand, natronlud, tetrahydrofuran eller dioxan ved temperaturer 25 mellem 0 og 80°C, dog fortrinsvis ved stuetemperatur.The subsequent alkylation is conveniently carried out with an alkyl halide such as methyl iodide or propyl bromide or a sulfonic acid ester such as dimethyl sulfate, preferably in the presence of a base such as sodium hydroxide or pyridine, optionally in the presence of a reaction accelerator such as tetrabutylammonium hydrogen sulfate and preferably methanol, ethanol, water, sodium hydroxide, tetrahydrofuran or dioxane at temperatures between 0 and 80 ° C, but preferably at room temperature.
udgangsmaterialer anvendte forbindelser med de almene formler II til XIV er delvis litteraturbekendte, eller man kan opnå disse ved kendte metoder (se eksemplerne A til 0).Starting materials used compounds of general formulas II to XIV are partially known in the literature or can be obtained by known methods (see Examples A to 0).
30 Således opnås f.eks. en hydroxyforbindelse med den almene formel II ved omsætning af en passsende carbonylforbindelse med et passende Grignard-forbin-delse med efterfølgende omsætning med phosgen og fra-spaltning af den som beskyttelsesgruppe for hydroxy-35 gruppen anvendte gruppe og en forbindelse med den almene formel V, ved efterfølgende omsætning af en 18Thus, e.g. a hydroxy compound of general formula II by reacting a suitable carbonyl compound with a suitable Grignard compound with subsequent reaction with phosgene and decomposing the group used as a protecting group for the hydroxy group and a compound of general formula V, by subsequent turnover of an 18
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således opnået hydroxy—4H-3,l-benzoxazin-2-on med en passende forbindelse, f.eks. med en passende monohalogen- eller dihalogenforbindelse. Endvidere opnås en forbindelse med den almene formel V også ved overfø-5 ring af hydroxygruppen i en passende forbindelse i en nucleofil fraspaltelig gruppe, f.eks. ved hjælp af thionylchlorid eller methansulfonylchlorid.thus obtained hydroxy-4H-3,1-benzoxazin-2-one with a suitable compound, e.g. with a suitable monohalogen or dihalogen compound. Furthermore, a compound of general formula V is also obtained by transferring the hydroxy group into a suitable compound in a nucleophilic leaving group, e.g. using thionyl chloride or methanesulfonyl chloride.
En forbindelse med den almene formel III opnås ved omsætning af en passende a, ω-disubstitueret alkan 10 med en passende mercaptoforbindelse og eventuelt efterfølgende oxidation.A compound of general formula III is obtained by reacting an appropriate α, ω-disubstituted alkane 10 with an appropriate mercapto compound and optionally subsequent oxidation.
En som udgangsmateriale anvendt forbindelse med de almene formler IV, VII eller XII opnås ved omsætning af en passende hydroxyforbindelse med den almene 15 formel II med en passende forbindelse. En således opnået forbindelse kan derefter ved oxidation overføres i en forbindelse med den almene formel IX eller XII.A starting compound used with the general formulas IV, VII or XII is obtained by reacting an appropriate hydroxy compound of the general formula II with a suitable compound. A compound thus obtained can then be transferred by oxidation into a compound of general formula IX or XII.
En som udgangsmateriale anvendt forbindelse med den almene formel VIII opnås f.eks. ved omsætning af 20 en passende O-carbonyl- eller O-sulfonylacethydroxy-myresyreester med svovlsyre og efterfølgende ekstraktion efter tilsætning af en base.A compound of general formula VIII used as starting material is obtained e.g. by reaction of an appropriate O-carbonyl or O-sulfonylacetydroxy formic acid ester with sulfuric acid and subsequent extraction after addition of a base.
En som udgangsmateriale anvendt forbindelse med den almene formel X opnås f.eks. ved omsætning af en 25 passende hydroxy- eller mercaptoforbindelse med et passende halogenid i nærværelse af en base.For example, a compound of the general formula X used as starting material is obtained. by reacting an appropriate hydroxy or mercapto compound with an appropriate halide in the presence of a base.
En som udgangsmateriale anvendt forbindelse med den almene formel XI opnås ved omsætning af et passende amid med et hypohalogenit, eventuelt i nærvæ-30 relse af en base.A starting compound used with the general formula XI is obtained by reacting a suitable amide with a hypohalogenite, optionally in the presence of a base.
En som udgangsmateriale anvendt forbindelse med den almene formel XIII opnås ved omsætning af en passende anthranilsyreester med en passende Grignard-forbindelse.A starting material used as a compound of general formula XIII is obtained by reacting a suitable anthranilic acid ester with a suitable Grignard compound.
35 Endvidere kan et således fremstillet udgangsmate riale med den almene formel II efterfølgende ved 19Further, a starting material of the general formula II thus prepared can subsequently be added at 19
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chlorering eller bromering, f.eks. ved hjælp af chlor, sulforylchlorid eller brom, overøres i den tilsvarende halogenforbindelse, eventuelt med salpetersyre i den tilsvarende nitroforbindelse.chlorination or bromination, e.g. by chlorine, sulforyl chloride or bromine is stirred in the corresponding halogen compound, optionally with nitric acid in the corresponding nitro compound.
5 Forbindelserne med den almene formel I, hvori AThe compounds of general formula I wherein A
er et svovlatom eller en R-N=S-gruppe, er værdifulde mellemprodukter til fremstilling af forbindelserne med den almene formel I, hvori A er en SO-, S02- eller R-N=S0-gruppe.is a sulfur atom or an R-N = S group, are valuable intermediates for preparing the compounds of general formula I wherein A is a SO, SO 2 or R-N = SO group.
10 Endvidere har de hidtil ukendte forbindelser med den almene formel I som nævnt tidligere værdifulde farmakologiske egenskaber, især antithrombotiske virkninger. De fremmer syntesen af aggregationshæmmende prostaglandiner i karvæggen. Forbindelserne med den 15 almene formel I har også en hæmmende virkning på tumormetastasering. Dette beror på de følgende egenskaber hos de ifølge opfindelsen fremstillede forbindelser: 1. De er hæmmere for blodpladephosphodiesterase, der er kendte som hæmmere for tumormetastaseringen (H.Furthermore, the novel compounds of the general formula I have, as mentioned previously, valuable pharmacological properties, especially antithrombotic effects. They promote the synthesis of aggregation-inhibiting prostaglandins in the vessel wall. The compounds of general formula I also have an inhibitory effect on tumor metastasis. This is due to the following properties of the compounds of the invention: 1. They are platelet phosphodiesterase inhibitors known as inhibitors of tumor metastasis (H.
20 Gastpar, Thrombosis Research j?, 277-289 (1974) og K.V. Honn, Science 212, 1270-1272 (1981)).Gastpar, Thrombosis Research, 277-289 (1974) and K.V. Hon. Science 212, 1270-1272 (1981)).
2. Forbindelserne hæmmer den primære hæmostase allerede ved meget lille dosering. Vedhæftningen af thrombo-cytter på beskadigede kar og dannelsen af en ren blod-25 pladethrombus undgås, hvilket fører til en stærk forlængelse af blødningstiden. Dette er for forbindelserne med formlen I ikke alene forklarligt ved en indskrænkning af blodpladefunktionen, men ved en yderligere forhøjet frigørelse af blodpladevirksomt PG gennem karrets endothel-30 celler. En bekræftelse herpå er udeblivelsen af blødningstidsforlængelse, såfremt prostacyclinsyntesen i en-dothelcellerne afbrydes med forinden indgivet cyclooxy-genasehæmmer. Forbindelserne frembyder således en hidtil endnu ubekendt optimal kombination af to virkningsprin-35 cipper, nemlig den forøgede syntese af thrombocytvirk-somme c.AmP-hævende PG'er gennem karvæggen og hæmning af 202. The compounds inhibit primary hemostasis already at very low dosage. The adherence of thrombocytes to damaged vessels and the formation of a clean blood platelet thrombus are avoided, leading to a strong prolongation of bleeding time. This is explained by the compounds of formula I not only by a restriction of platelet function, but by a further elevated release of platelet-active PG through the vessel's endothelial cells. A confirmation of this is the absence of bleeding time extension if the prostacyclin synthesis in the endothelial cells is interrupted with the previously administered cyclooxygenase inhibitor. Thus, the compounds present an unprecedented optimal combination of two principles of action, namely the increased synthesis of platelet-acting c.AmP-elevating PGs through the vessel wall and inhibition of 20
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nedbrydningen af det forøgede c.AinP gennem hæmning af PDE i thrombocytterne.the degradation of the increased c.AinP through inhibition of PDE in the platelets.
Den således erkendelige stigning i prostaglandin )-aktiviteten eller syntesen i karvæggen er ifølge 5 HONN (K.V. Honn, Science 212, 1270-1272 (1981)) lige ledes en årsag til hæmningen af tumormetastaseringen.According to 5 HONN (K.V. Honn, Science 212, 1270-1272 (1981)), the increase in prostaglandin activity or synthesis in the vessel wall is similarly caused by the inhibition of tumor metastasis.
F.eks. afprøvedes de følgende forbindelser A = 6-[4-(4-chlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-10 4H-3,l-benzoxazin-2-on, B = 6-[4-(4-hydroxy-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on, C = 6-[4-(4-methoxy-phenylsulfoximino)-butoxy]4,4-dimethyl-4H-3,l-benzoxazin-2-on, 15 D = 6-[4-(4-methyl-phenylsulfinyl)-butoxy]4,4-dimethyl-4H-3,l-benzoxazin-2-on, E = 6-[4-(4-cyclohexyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on, F = 6-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]4,4-di-20 methyl-4H-3,l-benzoxazin-2-on, G = 6-[4-(3-methoxy-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,1-benzoxazin-2-on, H = 6-[4-(4-fluor-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on, 25 I = 6-[4-(4-brom-phenylsulfoximino)-butoxy]-4,4-di-methy1-4H-3,1-benzoxazin-2-on, K = 6-(4-phenylsulfinyl-butoxy)-4H-3, l-benzoxazin-2-on, L = 6-[4-(4-brom-phenylsulfonyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on, 30 M = 6-[4-(4-brom-3-methyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on, N = 6-[4-(4-methyl-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on, 0 = 6-[4-(3,4-dimethoxy-phenylsulfoximino)-butoxy]-4,4-35 dimethyl-4H-3,l-benzoxazin-2-on, P = 6-[4-(4-amino-3,5-dibrom-phenylsulf inyl)-butoxy ]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on, 21Eg. the following compounds A = 6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, B = 6- [4- (4) -hydroxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, C = 6- [4- (4-methoxy-phenylsulfoxymino) -butoxy] 4.4- dimethyl-4H-3,1-benzoxazin-2-one, D = 6- [4- (4-methyl-phenylsulfinyl) -butoxy] 4,4-dimethyl-4H-3,1-benzoxazin-2-one, E = 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, F = 6- [4- (3,4-dichloro-2-one) phenylsulfoxymino) -butoxy] 4,4-dimethyl-4H-3,1-benzoxazin-2-one, G = 6- [4- (3-methoxy-phenylsulfoxymino) -butoxy] -4,4-di methyl 4H-3,1-benzoxazin-2-one, H = 6- [4- (4-fluoro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2-one one, 6- [4- (4-bromo-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, K = 6- (4-phenylsulfinyl-2-one) butoxy) -4H-3,1-benzoxazin-2-one, L = 6- [4- (4-bromo-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one , M = 6- [4- (4-bromo-3-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl 1-4H-3,1-benzoxazin-2-one, N = 6- [4- (4-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2-one one, O = 6- [4- (3,4-dimethoxy-phenylsulfoxymino) -butoxy] -4,4- 35 dimethyl-4H-3,1-benzoxazin-2-one, P = 6- [4- (4 -amino-3,5-dibromo-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, 21
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Q = 6-[4-(4-biphenylyl-sulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on, R = 6-[4-(3,4-dimethoxy-N-acetyl-phenylsulfoximino)-bu-toxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on, 5 S = 6-[4-(3,5-di-tert.butyl-4-hydroxy-N-acetyl-phenyl- sulfoximino)-butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on, T = 7-brom-4,4-dimethyl-6-[4-(4-methyl-phenylsulfoximi-no)-butoxy]-4H-3,l-benzoxazin-2-on, 10 u = 7-chlor-4,4-dimethyl-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4H-3,l-benzoxazin-2-on og V = 7-brom-6-[4-(3,4-dichlor-phenylsulfinyl)-butoxyj- 4,4-dimethyl-4H-3,l-benzoxazin-2-on for deres biologiske egenskaber som følger: 15 1. PDE-Hæmning:Q = 6- [4- (4-biphenylyl-sulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, R = 6- [4- (3,4-biphenylyl) dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, 5 S = 6- [4- (3,5-di-tert-butyl) -4-hydroxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, T = 7-bromo-4,4-dimethyl-6- [ 4- (4-methyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one, 10 µl = 7-chloro-4,4-dimethyl-6- [4- (4-methyl-benzoxazin-2-one) phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one and V = 7-bromo-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy-4,4-dimethyl-4H-3 , 1-benzoxazin-2-one for their biological properties as follows: 1. PDE inhibition:
Princip: c.AMP hydrolyseres af phosphodiesterase (PDE) fra forskellige kilder således også fra blodplader til AMP. Denne hydrolyse inhiberes koncentrationsafhæn-20 gigt af PDE-hæmmere.Principle: c.AMP is hydrolyzed by phosphodiesterase (PDE) from various sources, thus also from platelets to AMP. This hydrolysis is inhibited by concentration dependent concentration of PDE inhibitors.
Metode:Method:
Som phosphodiesterase anvendtes den ovenstående væske fra 10.000 x g på humanblodplader, som var ned-frosset med vand og atter optøet.As phosphodiesterase, the above liquid from 10,000 x g was used on human platelets which were frozen with water and thawed again.
25 0,3 ml af en blanding, der indeholdt 0,1 mol/li- ter trishydroxy-aminomethan (pH 7,4), 3 mmol/liter magnesiumchlorid, 1 mmol/liter AMP 1 ymol/liter ^H-cAMP (specifik aktivitet ca. 10 MBq/pmol), PDE samt de stoffer, der skulle undersøges eller vand for 30 kontrollen inkuberedes i 15 minutter ved 37°C.25 ml of a mixture containing 0.1 mole / liter of trishydroxyaminomethane (pH 7.4), 3 mmol / liter of magnesium chloride, 1 mmol / liter of AMP 1 µmol / liter of ³H-cAMP (specific activity (about 10 MBq / pmol), PDE as well as the substances to be examined or water for the control were incubated for 15 minutes at 37 ° C.
Inkubationen standsedes ved tilsætning af 0,5 ml zinksulfat (0,266 mol/liter) og 0,5 ml bariumhydroxid (0,226 mol/liter), bundfaldet afcentrifugeredes og den 35 i den ovenstående væske tilbageværende aktivitet af det ikke omsatte ^H-cAMP bestemtes. Ud fra sammenlig- 22The incubation was stopped by the addition of 0.5 ml of zinc sulfate (0.266 mol / liter) and 0.5 ml of barium hydroxide (0.226 mol / liter), the precipitate was centrifuged and the activity remaining in the above liquid of the unreacted 3 H-cAMP was determined. From comparison 22
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ning mellem stoftilsætningerne og kontroltilsætningerne beregnedes koncentrationen for en 50%1ig hæmningsvirkning (IC50) for det enkelte stof: 5 Stof lc50 [iJinol/1^ter) A 0,24 B 0,23 C 0,13 D 0,21 10 E 0,078 F 0,042 G 0,077 H 0,18 I 0,11 15 K 1,5 L 0,24 M 0,066 N 0,065 0 0,20 20 P 0,056 Q 0,0068 R 0,71 S 0,077 T 0.001 25 U 0,0034 V 0,0038 2. Antithrombotisk virkning.between the substance additives and the control additives, the concentration was calculated for a 50% inhibitory effect (IC50) for the individual substance: 5 Substance lc50 [iJinol / l) ter A 0.24 B 0.23 C 0.13 D 0.21 10 E 0.078 F 0.042 G 0.077 H 0.18 I 0.11 15 K 1.5 L 0.24 M 0.066 N 0.065 0 0.20 20 P 0.056 Q 0.0068 R 0.71 S 0.077 T 0.001 25 U 0.0034 V 0.0038 2. Antithrombotic effect.
Methodik.Methodik.
30 Thrombocytaggregationen måltes efter BORN's og CROSS's metode (J. Physiol. 170, 397 (1964)9 i blodplade-rigt plasma fra sunde forsøgspersoner. For at hæmme størkning tilsættes blodet natriumcitrat 3,14% i et volumenforhold på 1:10.Thrombocyte aggregation was measured according to the method of BORN and CROSS (J. Physiol. 170, 397 (1964) 9 in platelet-rich plasma from healthy subjects. To inhibit clotting, blood sodium citrate was added 3.14% in a 1:10 volume ratio.
35 Collagen-induceret aggregation.35 Collagen-induced aggregation.
2323
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Forløbet for aftagelse af blodpladesuspensionens optiske tæthed måles og registreres fotometrisk efter tilsætning af det aggregationsudløsende stof. Ud fra tæthedskurvens hældningsvinkel findes aggregations-5 hastigheden. Det punkt på kurven ved hvilket den største lysgennemtrængelighed foreligger tjener til beregning af den "optical density".The platelet suspension optical density reduction process is measured and recorded photometrically after addition of the aggregation triggering agent. From the slope of the density curve, the aggregation velocity is found. The point on the curve at which the greatest light permeability is available serves to calculate the "optical density".
Collagenmængden vælges så lille som muligt, men dog således at der fremkommer en irreversibelt løbende 10 reaktionskurve. Der anvendes det handelskendte collagen fra firmaet Hormonchemie, Munchen, Tyskland.The amount of collagen is chosen as small as possible, but so as to produce an irreversibly continuous 10 reaction curve. The well-known collagen from Hormonchemie, Munich, Germany is used.
Inden collagentilsætningen inkuberes plasmaet i hvert tilfælde i 10 minutter med stoffet ved 37°C.Prior to the collagen addition, the plasma is incubated in each case for 10 minutes with the substance at 37 ° C.
Ud fra de opnåede målinger beregnedes grafisk en 15 EC50/ åer angiver en 50%'ig ændring af den "optical density" udtrykt som en aggregationshæmning.From the measurements obtained a graphical calculation of a 15 EC 50 / s indicates a 50% change in the "optical density" expressed as an aggregation inhibition.
Den efterfølgende tabel indeholder de fundne resultater: 24The following table contains the results found:
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Stof ec50 [ μπιοί/literj A 0,34 B 0,23 C 0,27 5 D 0,33 E 0,32 F 0,21 G 0,27 H 0,32 10 I 0,33 K 1,90 L 0,42 M 0,25 N 0,22 15 0 0,27 P 0,55 Q 0,25 R 2,30 S 2,20 20 T 0,069 U 0,028 V 0,044 3. Bestemmelse af blødningstidens forlængelse.Fabric ec50 [μπιοί / literj A 0.34 B 0.23 C 0.27 5 D 0.33 E 0.32 F 0.21 G 0.27 H 0.32 10 I 0.33 K 1.90 L 0 , 42 M 0.25 N 0.22 15 0 0.27 P 0.55 Q 0.25 R 2.30 S 2.20 20 T 0.069 U 0.028 V 0.044 3. Determination of bleeding time extension.
25 Anmærkning.25 Note.
Såvel den menneskelige organisme som organismen hos varmblodige dyr har en sindrig mekanisme, der skal beskytte dem mod blodtab i tilfælde af beskadigelser.Both the human organism and the organism of warm-blooded animals have an ingenious mechanism to protect them from blood loss in the event of damage.
Dette system består af blodpladerne (thrombocyter), der 30 ved hjælp af klæbeegenskaber hurtigt skal "stoppe" en kardefekt og således foranledige den primære hæmostase. Udover denne rene cellulære blødningsstandsningsmekanisme har legemet et blodstørkningssystem. I dette system bringes plasmafaktorer (æggehvidestoflegemer) på 35 virksom form, der slutteligt omdanner det flydende plasmaf ibrinogen til en størknet fibrinmasse.This system consists of platelets (platelets) which, by means of adhesive properties, must quickly "stop" a cardiac defect and thus cause the primary hemostasis. In addition to this pure cellular bleeding arrest mechanism, the body has a blood clotting system. In this system, plasma factors (egg whites) are brought into active form, which ultimately converts the liquid plasma ibrinogen into a solidified fibrin mass.
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Den primære hæmostases system, der i det væsentlige udgøres af thrombocyterne og størkningssystemet kompletterer hinanden med det fælles mål virkningsfuldt at beskytte legemet mod blodtab.The primary hemostasis system, which is essentially the thrombocytes and the clotting system, complements each other with the common goal of effectively protecting the body from blood loss.
5 Ved mange sygdomme kan der også i et intakt kar system komme et tilløb til størkningsprocesser samt sammenklumpning af thrombocyter. Blodstørkningssystemets afsvækning med cumarin eller heparin er kendt og kan let måles ved hjælp af kendte blodstørkningsundersøgelser, 10 der under præparatindvirkning viser en forlængelse (plasmarecalcif.-tid, hurtig-bestemmelse, thrombocintid osv.).5 In many diseases, an intact vessel system can also be used for solidification processes and clumping of platelets. The attenuation of the blood-clotting system with coumarin or heparin is known and can be readily measured by known blood-clotting studies which, during preparation, show an extension (plasma calcification time, fast determination, thrombocin time, etc.).
Eftersom den første hurtige blodstandsning i tilfælde af en beskadigelse sker ved thrombocyterne, kan 15 thrombocyternes funktion ved fastlæggelse af en standardiseret beskadigelse bestemmes godt ved måling af blødningstiden. Den normale blødningstid udgør hos mennesker ca. 1 til 3 minutter, men det forudsættes, at der er ydelsesdygtige thrombocyter til stede i tilstrækkeligt 20 antal. Ved et normalt thrombocyttal angiver en forlænget blødningstid en afvigende thrombocytfunktion. Dette ses f.eks. ved nogle medfødte thombocytfunktionslidelser.Since the first rapid anesthesia in the event of a lesion occurs in the platelets, the function of the platelets in determining a standardized lesion can be well determined by measuring the bleeding time. The normal bleeding time in humans is approx. 1 to 3 minutes, but it is assumed that effective platelets are present in sufficient numbers. At a normal platelet count, a prolonged bleeding time indicates a deviating platelet function. This is seen e.g. in some congenital platelet disorders.
Vil man på den anden side forhindre thrombocyternes tendens til spontan sammenklumpning, med deraf følgende 25 kartillukninger i det arterielle system, med medikamenter, skal blødningstiden under stofpåvirkning følgelig ved en vellykket thrombocytvirksom behandling forlænges.On the other hand, if the tendency of the platelets to spontaneously clump, with the resultant 25 cartilage closures in the arterial system, with medications is prevented, the bleeding time under the influence of the drug must accordingly be prolonged by a successful platelet treatment.
For et thrombocytvirksomt stof må der altså forventes en forlængelse af blødningstiden og - da det plasmatiske 30 størkningssystem jo ikke berøres - en normal blodstørkningstid.Thus, for a platelet-active substance, an extension of the bleeding time and - since the plasmatic clotting system is not affected - a normal blood clotting time must be expected.
Litteratur: W.D. Keidel: Kurzgefasstes Lehrbuch der Phy-siologie, Georg Thieme Verlag Stuttgart, 1967, side 31: Der Blutstillungsvorgang.Literature: W.D. Keidel: Short-term textbook of physiology, Georg Thieme Verlag Stuttgart, 1967, page 31: Der Blutstillungsvorgang.
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Til bestemmelse af blødningstiden blev vågne mus indgivet de stoffer, der skulle undersøges i en dosis på 10 mg/kg p.o. Efter 1 time blev der fra hvert dyrs halespids afskåret ca. 0,5 mm, og det udtrædende blod blev 5 med intervaller på 30 sekunder indtil blødningens standsning forsigtigt afduppet med et filtrerpapir. Antallet af de således opnåede bloddråber giver et mål for blødningstiden (5 dyr pr. forsøg). De følgende talangi velser angiver den procentvise forlængelse i forhold til 10 kontroller uden stofindgivning:To determine the bleeding time, awake mice were administered the substances to be tested at a dose of 10 mg / kg p.o. After 1 hour, the tail tip of each animal was cut approx. 0.5 mm, and the withdrawing blood was gently dipped with a filter paper at intervals of 30 seconds until the bleeding stopped. The number of blood drops thus obtained gives a measure of the bleeding time (5 animals per trial). The following figures indicate the percentage increase over 10 controls without drug administration:
Stof Blødningstidens forlængelse i _ % efter 1 time A > 248 B > 263 15 C > 241 D > 250 E 46 F > 275 G > 245 20 H 46 X > 220 K 121 L > 266 M 100 25 N 63 0 > 227 P 73 Q 128 R > 241 30 S > 226 T 60 U > 230 V 100 27Substance Bleeding time extension in _% after 1 hour A> 248 B> 263 15 C> 241 D> 250 E 46 F> 275 G> 245 20 H 46 X> 220 K 121 L> 266 M 100 25 N 63 0> 227 P 73 Q 128 R> 241 30 S> 226 T 60 U> 230 V 100 27
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4. Akut toxicitet.4. Acute toxicity.
Den akutte toxicitet hos de stoffer, der skulle undersøges, bestemtes orienterende på grupper på hver 10 mus efter oral indgivning af en enkelt dosis (iagttagel-5 sestid: 14 dage):The acute toxicity of the substances to be tested was determined in groups of 10 mice after oral administration of a single dose (observation time: 14 days):
Stof_Orienterende akut toxicitet A 1000 mg (0 af 10 dyr døde) B 1000 mg (0 af 10 dyr døde) C 1000 mg (0 af 10 dyr døde) 10 D 1000 mg (0 af 10 dyr døde) E 1000 mg (0 af 10 dyr døde) R 1000 mg (0 af 10 dyr døde) S 1000 mg (0 af 10 dyr døde) T 1000 mg (0 af 10 dyr døde) U 1000 mg (0 af 10 dyr døde) V_1000 mg (0 af 10 dyr døde) På grund af deres farmakologiske egenskaber egner de hidtil ukendte forbindelser sig til behandling og prophylaxe af thrombo-emboliske lidelser såsom 20 coronarinfarkt, cerebralinfarkt, såkaldte transient ischaemic attacks, amaurosis fugax, til prophylaxe af arterioschlerose og til metastaseprophylaxe.Substance_Orienting acute toxicity A 1000 mg (0 of 10 animals dead) B 1000 mg (0 of 10 animals dead) C 1000 mg (0 of 10 animals dead) 10 D 1000 mg (0 of 10 animals dead) E 1000 mg (0 of 10 animals dead) R 1000 mg (0 of 10 animals dead) S 1000 mg (0 of 10 animals dead) T 1000 mg (0 of 10 animals dead) U 1000 mg (0 of 10 animals dead) V_1000 mg (0 of 10 Due to their pharmacological properties, the novel compounds are suitable for the treatment and prophylaxis of thromboembolic disorders such as 20 coronary infarction, cerebral infarction, so-called transient ischaemic attacks, amaurosis fugax, for prophylaxis of arteriosclerosis and for metastasis prophylaxis.
5. Sammenligning af henholdsvis antithrombotisk virkning og PDE-hæmning for forbindelser fremstillet ifølge op- 25 findelsen og for nærmest stående kendte forbindelser:5. Comparison of antithrombotic activity and PDE inhibition, respectively, for compounds prepared according to the invention and for closest known compounds:
Nedenstående omhandlede forbindelser A-H og sammenligningsforbindelser A-H' samt F" blev som ovenfor beskrevet under punkterne 2 og 1 sammenlignet, hvad angår antithrombotisk virkning og PDE-hæmning.The following compounds Compounds A-H and Comparative Compounds A-H 'and F "were compared as described above under points 2 and 1 in terms of antithrombotic activity and PDE inhibition.
30 ' A = 6—[4 —(4-chlorphenylsulfinyl)butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-3-on (se forbindelse A) A' = 6-[4-(4-chlorphenylsulfinyl)butoxy]-3,4-dihydrocar-bostyril (se forbindelse I i EP-A-3.771) B = 6—[4 —{4-cyclohexylphenylsulfinyl)butoxy]-4,4-dime-thyl-4H-3,1-benzoxazin-2-on (se forbindelse E) 2830 'A = 6- [4- (4-Chlorophenylsulfinyl) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-3-one (see compound A) A' = 6- [4- (4- chlorophenylsulfinyl) butoxy] -3,4-dihydrocar-bostyril (see compound I of EP-A-3,771) B = 6- [4- (4-cyclohexylphenylsulfinyl) butoxy] -4,4-dimethyl-4H-3, 1-benzoxazin-2-one (see compound E) 28
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B' = 6-[4-(4-cyclohexylphenylsulfinyl)butoxy]-3,4-dihy-drocarbostyril (se eksempel 204 i EP-A-3.771) C = 6-(4-phenylsulfinylbutoxy)-4H-3,1 -benzoxazin-2-on (se forbindelse K) 5 C = 6-(4-phenylsulfinylbutoxy)-3,4-dihydrocarbostyril (se forbindelse B i EP-A-3.771) D = 6—[4—(3,4-dichlorphenylsulfoximo)butoxy]-4,4-dime-thyl-4H-3,1-benzoxazin-2-on (se Eksempel 295) D' = 6—[4—(3,4-dichlorphenylsulfoximo)butoxy1-3,4-dihy-10 drocarbostyril (se eksempel 2 i EP-A-71.150) E = 6-[4-(4-chlorphenylsulfoximo)butoxy]-4,4,8-trime-thyl-4H-3,1-benzoxazin-2-on (se Eksempel 336) E' = 6-[4-(4-chlorphenylsulfoximo)butoxy]-3,4-dihydrocarbostyril (se eksempel 9 i EP-A-71.150) 15 F = 6-[.4-(3,4-dimethoxyphenylsulfoximo)butoxy]-4,4,8-trimethyl-4H-3,1-benzoxazin-2-on (se Eksempel 332) F1 = 6-[4-(3,4-dimethoxyphenylsulfoximo)butoxy]-3,4-dihydrocarbostyril (se eksempel 84 i EP-A-71.150) F" = 3,3-dimethyl-5-[4-(3,4-dimethoxyphenylsulfoximo)-20 butoxy]indolinon-(2) (se eksempel 43 i EP-A-71.150) G = 6-[4-(3,4-dimethylphenylsulfoximo)butoxy]-4,4,8- trimethyl-4H-3,1-benzoxazin-2-on (se Eksempel 333) G1 = 3,3-dimethyl-5-[ 3,4-dimethylphenylsulfoximo) butoxy ]-indolinon-(2) (se eksempel 121 i EP-A-71.150) 25 h = 6-[4-(3,4-dichlor-N-acetylphenylsulfoximo)butoxy]- 4.4- dimethyl-4H-3,1-benzoxazin-2-on (se Eksempel 296), og H* = 6-[4-(N-acetyl-3,4-dichlorphenylsulfoximo)butoxy]- 3.4- dihydrocarbostyril (se eksempel 47 i EP-A-71.150) 30B '= 6- [4- (4-cyclohexylphenylsulfinyl) butoxy] -3,4-dihydrocarbostyril (see Example 204 in EP-A-3,771) C = 6- (4-phenylsulfinylbutoxy) -4H-3.1 - benzoxazin-2-one (see compound K) 5 C = 6- (4-phenylsulfinylbutoxy) -3,4-dihydrocarbostyril (see compound B of EP-A-3,771) D = 6- [4- (3,4-dichlorophenylsulfoxime) ) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one (see Example 295) D '= 6- [4- (3,4-dichlorophenylsulfoxymo) butoxy] -3,4-dihy -10 drocarbostyril (see Example 2 of EP-A-71,150) E = 6- [4- (4-Chlorophenylsulfoxime) butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one (see Example 336) E '= 6- [4- (4-Chlorophenylsulfoxime) butoxy] -3,4-dihydrocarbostyril (see Example 9 of EP-A-71,150) F = 6 - [. 4- (3.4 -dimethoxyphenylsulfoxime) butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one (see Example 332) F1 = 6- [4- (3,4-dimethoxyphenylsulfoxime) butoxy] -3,4 dihydrocarbostyril (see Example 84 of EP-A-71,150) F "= 3,3-dimethyl-5- [4- (3,4-dimethoxyphenylsulfoxymo) -butoxy] indolinone (2) (see Example 43 of EP A-71.150) G = 6- [4- (3.4 -dimethylphenylsulfoxymol) butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one (see Example 333) G1 = 3,3-dimethyl-5- [3,4-dimethylphenylsulfoxymol) butoxy] - indolinone- (2) (see Example 121 of EP-A-71,150) h = 6- [4- (3,4-dichloro-N-acetylphenylsulfoxime) butoxy] -4,4-dimethyl-4H-3,1-benzoxazine 2-one (see Example 296), and H * = 6- [4- (N-acetyl-3,4-dichlorophenylsulfoxime) butoxy] -3,4-dihydrocarbostyril (see Example 47 in EP-A-71,150)
Man opnåede herved følgende resultater: 35 29The following results were obtained: 35 29
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Antithrombotisk virkningAntithrombotic effect
Forbindelse E^50 ^ 5 A 0,34 A' 4,0 B 0,32 B' 3,4 10______________________________________________ C 1,90 C 4,0 D 0,21 15 D' 2,3 E 0,039 E' 3,2 20 F 0,03 F* 3,2 F' 1 0,46 G 0,027 25 G' 0,36 H 3,0 H' 6,0 30 30Compound E 50 50 A 0.34 A 4.0 B 0.32 B 3.4 3.4 1.90 C 4.0 D 0.21 D 2.3 E 0.039 E 3.2 20 F 0.03 F * 3.2 F '1 0.46 G 0.027 25 G' 0.36 H 3.0 H '6.0 30 30
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PDE-hæmningPDE Inhibition
Forbindelse IC50 ^ 5 A 0,24 A’ 0,8 B 0,078 B' 1,6 10_________________________________________________ C 1,5 C' 1,9 D 0,0042 15 D' 0,31 E 0,016 E* 0,84 20 F 0,0082 F' 1,6 F'1 0,28 G 0,0040 25 G' 0,07 H 0,22 H1 * 0,84 30Compound IC 50 5 A 0.24 A 0.8 B 0.078 B 1.6 1.5 C 1.5 C 1.9 D 0.0042 D 0.31 E 0.016 E * 0.84 F , 0082 F '1.6 F'1 0.28 G 0.0040 25 G' 0.07 H 0.22 H1 * 0.84
For de afprøvede forbindelser fremstillet ifølge opfindelsen ses for begge virkninger fra overlegenhed til tydelig overlegenhed i forhold til de tilsvarende kendte forbindelser.For the tested compounds prepared according to the invention, both effects are seen from superior to clear superior to the corresponding known compounds.
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Den til opnåelse af en passende virkning nødvendige dosering udgør hensigtsmæssigt to til fire gange dagligt 0,3 til 4 mg/kg legemsvægt, fortrinsvis 0,3 til 2 mg/kg legemsvægt. Hertil kan de ifølge opfindelsen 5 fremstillede forbindelser med den almene formel I eventuelt i kombination med andre virksomme stoffer oparbejdes sammen med et eller flere inerte almindelige bærestoffer og/eller fortyndingsmidler, f.eks. med majsstivelse, mælkesukker, rørsukker, mikrokrystallinsk cel-10 lulose, magnesiumstearat, polyvinylpyrrolidon, citronsyre, vinsyre, vand, vand/ethanol, vand/glycerin, vand/sorbit, vand/polyethylenglycol, propylenglycol, ce-tylstearylalkohol, carboxymethylcellulose eller fedtholdige stoffer såsom hårdt fedt eller egnede blandinger 15 deraf, til almindelige galeniske præparater såsom tabletter, drageer, kapsler, pulvere, suspensioner eller stikpiller.Conveniently, the dosage required to achieve an effective effect is 0.3 to 4 mg / kg body weight two to four times daily, preferably 0.3 to 2 mg / kg body weight. To this end, the compounds of the general formula I according to the invention may optionally be worked up in combination with other active substances together with one or more inert ordinary carriers and / or diluents, e.g. with corn starch, milk sugar, cane sugar, microcrystalline cellulose, magnesium stearate, polyvinylpyrrolidone, citric acid, tartaric acid, water, water / ethanol, water / glycerine, water / sorbit, water / polyethylene glycol, propylene glycol, cetyl stearyl alcohol, hard fat or suitable mixtures thereof, for common galenic preparations such as tablets, dragons, capsules, powders, suspensions or suppositories.
De efterfølgende eksempler belyser opfindelsen nærmere: 20The following examples further illustrate the invention:
Fremstilling af udgangsmaterialersPreparation of starting materials
Eksempel AExample A
6-Methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on.6-methoxy-4,4-dimethyl-4H-3, l-benzoxazin-2-one.
25 a) 2-Amino-5-methoxy~phenyl-dimethyl-carbinol.A) 2-Amino-5-methoxy-phenyl-dimethyl-carbinol.
Under omrøring dryppedes en opløsning af 261 ml (4,2 mol) methyliodid i 1000 ml absolut ether til en suspension af 102 g (4,2 mol) magnesiumspåner i 300 ml absolut ether indenfor 2,5 timer og efteromrørtes i yder-30 ligere en \ time. Derefter tildryppedes der i løbet af \ time under afkøling - for at temperaturen ikke steg over 20 til 25°C - en opløsning af 181,2 g (1 mol) 5-methoxy-anthranilsyre-methylester i 1,5 liter absolut ether.With stirring, a solution of 261 ml (4.2 moles) of methyl iodide in 1000 ml of absolute ether was dropped to a suspension of 102 g (4.2 moles) of magnesium chips in 300 ml of absolute ether within 2.5 hours and stirred further. one hour. Then, during cooling, - in order that the temperature did not rise above 20 to 25 ° C - drop a solution of 181.2 g (1 mole) of 5-methoxy-anthranilic acid methyl ester in 1.5 liters of absolute ether.
Efter 1 times efteromrøring hældtes blandingen over i 35 32After 1 hour of stirring, the mixture was poured into 35 32
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ammoniumchloridholdigt isvand, etherfasen isoleredes, vaskedes med anunoniumchloridholdigt vand, tørredes med natriumsulfat, og etheren afdestilleredes.ammonium chloride-containing ice water, the ether phase was isolated, washed with anunonium chloride-containing water, dried over sodium sulfate and the ether distilled off.
b) 6-Methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on.b) 6-Methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Den efter afdestillering af etheren tilbageblevne rest af 2-amino-5-methoxy-phenyl-dimethyl-carbinol opløstes uden yderligere rensning i 1,5 liter chloroform, tilsattes 276,4 g (2 mol) kaliumcarbonat og opvarmedes til 40°C. Til denne opløsning dryppedes i løbet af 2 ti-10 mer 600 ml 2%*ig opløsning af phosgen i toluen (1,2 mol) så hurtigt, at reaktionsblandingens temperatur udgjorde mellem 40 og 50°C, herved kan der forekomme en eventuel opskumning. Efter afsluttet tilsætning henstilledes blandingen natten over ved stuetemperatur.The residue of 2-amino-5-methoxy-phenyl-dimethyl-carbinol, after distilling off the ether, was dissolved without further purification in 1.5 liters of chloroform, 276.4 g (2 moles) of potassium carbonate added and heated to 40 ° C. To this solution, 600 ml of 2% * solution of phosgene in toluene (1.2 mol) was added dropwise over 2 hours to a temperature of the reaction mixture between 40 and 50 ° C, thereby causing any foaming . After completion of the addition, the mixture was allowed to stand overnight at room temperature.
15 Derefter tilsattes 1 liter vand, chloroform/to luen-fasen isoleredes, den vandige fase ekstraheredes flere gange med chloroform, til hvilken der var sat lidt methanol. De samlede organiske ekstrakter vaskedes med vand, tørredes med natriumsulfat, og opløsningsmidlet 20 fradestilleredes. Den krystallinske rest omkrystalliseredes i toluen/eddikesyreethylester = 9:1.Then 1 liter of water was added, the chloroform / two luen phase was isolated, the aqueous phase extracted several times with chloroform to which little methanol was added. The combined organic extracts were washed with water, dried over sodium sulfate and the solvent was distilled off. The crystalline residue was recrystallized from toluene / acetic acid ethyl ester = 9: 1.
Smp.: 182-183°C.Mp: 182-183 ° C.
Udbytte: 130 g (64% af det teoretiskes i forhold til den anvendte 5-methoxy-anthranilsyre-methylester).Yield: 130 g (64% of theory relative to the 5-methoxy-anthranilic acid methyl ester used).
25 På tilsvarende vis opnåedes de følgende forbin delser: 6-methoxy-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on ud fra 5- methoxy-anthranilsyre-methylester, n-hexyl-magnesium-bromid og phosgen.Similarly, the following compounds were obtained: 6-methoxy-4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one from 5-methoxy-anthranilic acid methyl ester, n-hexyl-magnesium -bromide and phosgene.
30 Smp.: 101-103°C.Mp: 101-103 ° C.
Udbytte: 70,8% af det teoretiske.Yield: 70.8% of theory.
6- methoxy-4,4-diphenyl-4H-3,l-benzoxazin-2-on ud fra 5-methoxy-anthranilsyre-methylester, phenylmagnesium- 35 bromid og phosgen.6- Methoxy-4,4-diphenyl-4H-3,1-benzoxazin-2-one from 5-methoxy-anthranilic acid methyl ester, phenylmagnesium bromide and phosgene.
Smp.: 237°C.Mp: 237 ° C.
Udbytte: 69,5% af det teoretiske.Yield: 69.5% of theory.
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6-methoxy-4,4-dicyclohexyl-4H-3, l-benzoxazin-2-on ud fra 5- methoxy-anthranilsyre-methylester, cyclohexylmagnesi-umbromid og phosgen. Smp.: 269-271°C.6-methoxy-4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one from 5-methoxy-anthranilic acid methyl ester, cyclohexylmagnesium bromide and phosgene. Mp: 269-271 ° C.
Udbytte: 50,4% af det teoretiske.Yield: 50.4% of theory.
5 6- methoxy-4-isopropyl-4H-3, l-benzoxazin-2-on ud fra 5-methoxy-2-amino-benzaldehyd (fremstillet ud fra 5- methoxy-2-nitro-benzaldehyd og Pt/H2 ved 30 bar og 35°C), isopropylmagnesiumiodid og phosgen.5-Methoxy-4-isopropyl-4H-3,1-benzoxazin-2-one from 5-methoxy-2-amino-benzaldehyde (prepared from 5-methoxy-2-nitro-benzaldehyde and Pt / H2 at 30 bar and 35 ° C), isopropylmagnesium iodide and phosgene.
10 Smp.: 124-125°C.Mp: 124-125 ° C.
Udbytte: 37,1% af det teoretiske.Yield: 37.1% of theory.
6- methoxy-4-ethyl-4H-3, l-benzoxazin-2-on ud fra 5-me-thoxy-2-amino-benzaldehyd, ethylmagnesiumbromid og phos- "•S gen.6- methoxy-4-ethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-2-amino-benzaldehyde, ethylmagnesium bromide and phos- • S gene.
Smp.: 88-89°C.Mp: 88-89 ° C.
Udbytte: 30,2% af det teoretiske.Yield: 30.2% of theory.
6-methoxy-*4-phenyl-4H-3, l-benzoxazin-2-on ud fra 5-me-20 thoxy-2-amino-benzaldehyd, phenylmagnesiumbromid og phosgen.6-Methoxy-4-phenyl-4H-3,1-benzoxazin-2-one from 5-methoxy-2-amino-benzaldehyde, phenylmagnesium bromide and phosgene.
Smp.: 157-158°C.Mp: 157-158 ° C.
Udbytte: 36,3% af det teoretiske.Yield: 36.3% of theory.
25 6-methoxy-4,4-diethyl-4H-3,l-benzoxazin-2-on ud fra 5- methoxy-anthranilsyre-methylester, ethylmagnesiumbromid og phosgen.6-Methoxy-4,4-diethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-anthranilic acid methyl ester, ethylmagnesium bromide and phosgene.
Smp.: 123-125°C.Mp: 123-125 ° C.
Udbytte: 90,1% af det teoretiske.Yield: 90.1% of theory.
30 6- methoxy-4-methyl-4H-3, l-benzoxazin-2-on ud fra 5-me-thoxy-2-amino-benzaldehyd, methylmagnesiumiodid og phosgen.6- methoxy-4-methyl-4H-3,1-benzoxazin-2-one from 5-methoxy-2-amino-benzaldehyde, methylmagnesium iodide and phosgene.
Smp.: 120-121°C.Mp: 120-121 ° C.
Udbytte: 20,2% af det teoretiske.Yield: 20.2% of theory.
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5- methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on ud fra 6- methoxy-anthranilsyre-methylester, methylmagnesium-iodid og phosgen.5- Methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one from 6- methoxy-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.
Smp.: 139-141°C.Mp: 139-141 ° C.
5 Udbytte: 22% af det teoretiske.Yield: 22% of theory.
7- methoxy-4,4-dimethyl-4H-3, l-benzoxazin-2-on ud fra 4- methoxy-anthranilsyre-methylester, methylmagnesium-iodid og phosgen.7- Methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one from 4-methoxy-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.
TO Smp.: 119-121°C.TO mp: 119-121 ° C.
Udbytte: 62% af det teoretiske.Yield: 62% of theory.
8- methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on ud fra 15 3-methoxy-anthranilsyre-methylester, methylmagnesium- iodid og phosgen.8- Methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one from 3-methoxy-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.
Smp.: 95-96°C.Mp: 95-96 ° C.
Udbytte: 42,1% af det teoretiske.Yield: 42.1% of theory.
20 6-methoxy-4,4,7-trimethyl-4H-3,1-benzoxazin—2-on ud fra 5- methoxy-4-methyl-anthranilsyre-methylester, methyl-magnesiumiodid og phosgen.6-Methoxy-4,4,7-trimethyl-4H-3,1-benzoxazine-2-one from 5-methoxy-4-methyl-anthranilic acid methyl ester, methyl-magnesium iodide and phosgene.
Smp.: 134-135°C.Mp: 134-135 ° C.
Udbytte: 45,5% af det teoretiske.Yield: 45.5% of theory.
25 6- methoxy-4,4,8-trimethyl-4H-3, l-benzoxazin-2-on ud fra 5- methoxy-3-methyl-anthranilsyre-methylester, methyl-magnesiumiodid og phosgen.6- methoxy-4,4,8-trimethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-3-methyl-anthranilic acid methyl ester, methyl-magnesium iodide and phosgene.
Smp.: 218-219°C.Mp: 218-219 ° C.
30 Udbytte: 65,8% af det teoretiske.Yield: 65.8% of theory.
6- methoxy-5,7-dichlor-4,4-dimethyl-4H-3,l-benzoxazin-2-on ud fra 5-methoxy-4,6-dichlor-anthranilsyre-methyl-ester, methylmagnesiumiodid og phosgen.6- Methoxy-5,7-dichloro-4,4-dimethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-4,6-dichloro-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.
35 Smp.: 203-204°C.Mp: 203-204 ° C.
Udbytte: 44,0% af det teoretiske.Yield: 44.0% of theory.
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6-methoxy-5,7-dimethyl-4H-3,l-benzoxazin-2-on ud fra 5- methoxy-4,6-dimethyl-anthranilsyre-methylester, me-thylmagnesiumiodid og phosgen.6-Methoxy-5,7-dimethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-4,6-dimethyl-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.
Smp.: 152-153°C.Mp: 152-153 ° C.
5 Udbytte: 38,7% af det teoretiske.Yield: 38.7% of theory.
Eksempel BExample B
6- Methoxy-4H-3,l-benzoxazin-2-on.6- Methoxy-4H-3,1-benzoxazin-2-one.
a) 2-Amino-5-methoxy-benzylalkohol.a) 2-Amino-5-methoxy-benzyl alcohol.
]0 181,2 g (1 mol) 5-methoxy-2-nitro-benzaldehyd (fremstillet ved methylering af 2-nitro-5-hydroxy-benz-aldehyd med methyliodid/kalium-tert.butylat i dimethyl-sulfoxid) opløstes i 1/8 liter methanol, tilsattes 50 g Raney-nikkel og hydrogeneredes ved stuetemperatur og 5 15 bar. Efter 10 timer var hydrogenoptagelsen afsluttet. Katalysatoren sugedes fra og methanolet afdestilleredes.] 0 181.2 g (1 mole) of 5-methoxy-2-nitro-benzaldehyde (prepared by methylation of 2-nitro-5-hydroxy-benz-aldehyde with methyl iodide / potassium tert.butylate in dimethyl sulfoxide) were dissolved in 1/8 liter of methanol, 50 g of Raney nickel was added and hydrogenated at room temperature and 5 bar. After 10 hours, hydrogen uptake was complete. The catalyst was suctioned off and the methanol was distilled off.
b) 6-Methoxy-4H-3,l-benzoxazin-2-on.b) 6-Methoxy-4H-3,1-benzoxazin-2-one.
Den efter afdestillering af methanolet tilbageblevne rest opløstes uden yderligere rensning i 1 liter 20 chloroform og tilsattes 175 g (1,25 mol) kaliumcarbonat.The residue remaining after distilling off the methanol was dissolved in 1 liter of chloroform without further purification and 175 g (1.25 mole) of potassium carbonate was added.
Til denne suspension dryppedes ved 50°C under omrøring 553 ml (1,05 mol) 20%'ig opløsning af phosgen i toluen forsigtigt. Efter 2 timers efteromrøring ved stuetemperatur hældtes blandingen over i isvand, chloroform/tolu-25 en-fasen separeredes, og den vandige fase ekstraheredes flere gange med chloroform/methanol * 5/1. De samlede organiske ekstrakter vaskedes med vand, tørredes med natriumsulfat, og opløsningsmidlet fradestilleredes.To this suspension, 553 ml (1.05 mole) of 20% solution of phosgene in toluene was gently dropped at 50 ° C with stirring. After 2 hours of stirring at room temperature, the mixture was poured into ice water, the chloroform / toluene phase was separated and the aqueous phase extracted several times with chloroform / methanol * 5/1. The combined organic extracts were washed with water, dried over sodium sulfate and the solvent was distilled off.
Resten rensedes søjlechromatografisk (kiselgel, chloro-30 form/acetone = 19:1). De efter afdestillering af elue-ringsmidlet tilbageblevne krystaller smeltede ved 154-156°C.The residue was purified by column chromatography (silica gel, chloroform / acetone = 19: 1). The crystals remaining after distilling off the eluent melted at 154-156 ° C.
Udbytte: 110,5 g (61,7% af det teoretiske).Yield: 110.5 g (61.7% of theory).
3 5 Analogt opnåedes den følgende forbindelse: 6-methoxy-7-chlor~4H-3,l-benzoxazin-2-on.Analogously, the following compound was obtained: 6-methoxy-7-chloro-4H-3,1-benzoxazin-2-one.
Smp.: 208-210°C.Mp: 208-210 ° C.
Udbytte: 38,7% af det teoretiske.Yield: 38.7% of theory.
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3636
Eksempel CExample C
6-Hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on.6-hydroxy-4,4-dimethyl-4H-3, l-benzoxazin-2-one.
237,5 g (1,146 mol) 6-methoxy-4,4-dimethyl-4H- 3,l-benzoxazin-2-on opløstes i 2,4 liter tørt ethylen-5 chlorid og tilsattes under omrøring ved -30 til -40°C dråbevis 125 ml (330,3 g = bortribromid. Efter afsluttet tilsætning opvarmedes der til stuetemperatur, og blandingen henstilledes natten over. Herefter tildryppedes under afkøling og omrøring 1 liter 50%'ig ethanol, blan-10 dingen reduceredes til ca. 500 ml og fortyndedes med 3 liter vand. Det udfældede bundfald afsugedes og tørredes.237.5 g (1.146 moles) of 6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one were dissolved in 2.4 liters of dry ethylene chloride and added with stirring at -30 to -40 C drop dropwise 125 ml (330.3 g = boron tribromide. After completion of addition, warmed to room temperature and allowed to stand overnight. Then, after cooling and stirring, 1 liter of 50% ethanol was added dropwise, the mixture was reduced to about 500 ml and diluted with 3 liters of water. The precipitated precipitate was aspirated and dried.
Smp.: 202-204°C (fra eddikesyreethylester/petrole- umsether).Mp: 202-204 ° C (from acetic acid ethyl ester / petroleum ether).
15 Udbytte: 223,3 g (99,8% af det teoretiske).Yield: 223.3 g (99.8% of theory).
Analogt opnåedes de følgende forbindelser: 6-hydroxy-4H-3,l-benzoxazin-2-on.Analogously, the following compounds were obtained: 6-hydroxy-4H-3,1-benzoxazin-2-one.
20 Smp.s 244-245°C.Mp 244-245 ° C.
Udbytte: 78,5% af det teoretiske.Yield: 78.5% of theory.
6-hydroxy-4,4-di-n-hexyl-4H-3,1-benzoxazin-2-on.6-hydroxy-4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Smp.: 144-146°C.Mp: 144-146 ° C.
25 Udbytte: 92,4% af det teoretiske.Yield: 92.4% of theory.
6-hydroxy-4,4-diphenyl-4H-3,l-benzoxazin-2-on.6-hydroxy-4,4-diphenyl-4H-3, l-benzoxazin-2-one.
Smp.: 239°C (sønderdeling).Mp: 239 ° C (dec.).
Udbytte: 90,0% af det teoretiske.Yield: 90.0% of theory.
30 6-hydroxy-4-isopropyl-4H-3,l-benzoxazin-2-on.6-hydroxy-4-isopropyl-4H-3,1-benzoxazin-2-one.
Smp.: 215-216°C.Mp: 215-216 ° C.
Udbytte:77,6% af det teoretiske.Yield: 77.6% of theory.
6-hydroxy-4-ethyl-4H-3,l-benzoxazin-2-on.6-hydroxy-4-ethyl-4H-3, l-benzoxazin-2-one.
Smp.: 216-218°C.Mp: 216-218 ° C.
Udbytte: 68,5% af det teoretiske.Yield: 68.5% of theory.
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6-hydroxy-4,4-dicyclohexy1-4H-3,1-benzoxazin-2-on.6-hydroxy-4,4-dicyclohexy1-4H-3,1-benzoxazin-2-one.
Smp.: > 280°C.Mp:> 280 ° C.
Udbytte: 97,8% af det teoretiske 6-hydroxy-4,4-diethyl-4H-3,l-benzoxazin-2-on.Yield: 97.8% of theoretical 6-hydroxy-4,4-diethyl-4H-3,1-benzoxazin-2-one.
5 Smp.: 194-195°C.Mp: 194-195 ° C.
Udbytte: 95,5% af det teoretiske.Yield: 95.5% of theory.
6- hydroxy-4-methyl-4H-3, l-benzoxazin-2-on.6- hydroxy-4-methyl-4H-3,1-benzoxazin-2-one.
Smp.: 226°C.Mp: 226 ° C.
10 Udbytte: 75,8% af det teoretiske.Yield: 75.8% of theory.
7- hydroxy~4,4-dimethyl-4H-3, l-benzoxazin-2-on.7- hydroxy ~ 4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 180-182°C.Mp: 180-182 ° C.
Udbytte: 96,8% af det teoretiske.Yield: 96.8% of theory.
15 5- hydroxy-4,4-dimethyl-4H-3, l-benzoxazin-2-on.5-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 251°C.Mp: 251 ° C.
Udbytte: 79% af det teoretiske.Yield: 79% of theory.
20 8-hydroxy~4,4-dimethyl-4H-3, l-benzoxazin-2-on.8-hydroxy ~ 4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 203-205°C.Mp: 203-205 ° C.
Udbytte: 90% af det teoretiske.Yield: 90% of theory.
6- hydroxy-4,4,8-trimethyl-4H-3, l-benzoxazin-2-on.6- hydroxy-4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
25 Smp.: 174°C (sønderdeling).Melting point: 174 ° C (dec.).
Udbytte: 94,3% af det teoretiske.Yield: 94.3% of theory.
6 -hydroxy-4,4,7 - tr imethy 1-4H-3,1 -benzoxaz in-2 -on.6-Hydroxy-4,4,7-trimethyl 1-4H-3,1-benzoxazin-2-one.
Smp.: 150-152°C.Mp: 150-152 ° C.
30 Udbytte: 85,8% af det teoretiske.Yield: 85.8% of theory.
8-chlor-6-hydroxy-4,4-dimethyl-4H-3, l-benzoxazin-2-on.8-Chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 196-198°C.Mp: 196-198 ° C.
Udbytte: 52% af det teoretiske.Yield: 52% of theory.
35 7- chlor-6-hydroxy-4, 4-dimethyl-4H-3, l-benzoxazin-2-on.7- Chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 218-219°C.Mp: 218-219 ° C.
Udbytte: 97,1% af det teoretiske.Yield: 97.1% of theory.
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7- brom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on.7- Bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 157-158°C.Mp: 157-158 ° C.
Udbytte: 96% af det teoretiske.Yield: 96% of theory.
8- brom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on.8- Bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Smp.: 212-214°C.Mp: 212-214 ° C.
Udbytte: 46,7% af det teoretiske.Yield: 46.7% of theory.
7,8-dibrom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on.7,8-dibromo-6-hydroxy-4,4-dimethyl-4H-3, l-benzoxazin-2-one.
10 Smp.: 194-195°C.Mp: 194-195 ° C.
Udbytte: 24% af det teoretiske.Yield: 24% of theory.
6-hydroxy-7-chlor-4H-3,l-benzoxazin-2-on.6-hydroxy-7-chloro-4H-3, l-benzoxazin-2-one.
Smp.: 250°C (sønderdeling).Mp: 250 ° C (dec.).
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Udbytte: 96,2% af det teoretiske.Yield: 96.2% of theory.
6-hydroxy-5,7-dichlor-4,4-dimethyl-4H-3,l-benzoxazin-2-on.6-hydroxy-5,7-dichloro-4,4-dimethyl-4H-3, l-benzoxazin-2-one.
Smp.: 215-217°C.Mp: 215-217 ° C.
2020
Udbytte: 88,0% af det teoretiske.Yield: 88.0% of theory.
6-hydrox-5,7-dimethyl-4H-3,l-benzoxazin-2-on.6-hydrox-5,7-dimethyl-4H-3, l-benzoxazin-2-one.
Smp.: 210-211°C.Mp: 210-211 ° C.
Udbytte: 70,5% af det teoretiske.Yield: 70.5% of theory.
2525
Eksempel DExample D
6-(5-Brom-pentoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on.6- (5-Bromo-pentoxy) -4,4-dimethyl-4H-3, l-benzoxazin-2-one.
En opløsning af 19,3 g (0,1 mol) 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on i 200 ml dimethylsulf-oxid tilsattes ved stuetemperatur 41,5 g (0,3 mol) ka-liumcarbonat og 92 g (0,4 mol) 1,5-dibrom-pentan, herved steg temperaturen til 45°C. Efter 2 timers efteromrøring tilsattes isvand og ekstraheredes med chloroform. Chlo- roformfasen vaskedes med vand, tørredes med natriumsul- 35 fat, og chloroformen afdestilleredes. Resten omkrystalliseredes i eddikesyreethylester/petroleumsether.A solution of 19.3 g (0.1 mol) of 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one in 200 ml of dimethyl sulfoxide was added at room temperature 41.5 g (0, 3 moles of potassium carbonate and 92 g (0.4 moles) of 1,5-dibromo-pentane, thereby raising the temperature to 45 ° C. After 2 hours of stirring, ice water was added and extracted with chloroform. The chloroform phase was washed with water, dried over sodium sulfate and the chloroform distilled off. The residue was recrystallized from acetic acid ethyl ester / petroleum ether.
Smp.: 113-115°C.Mp: 113-115 ° C.
Udbytte: 26,9 g (78,6% af det teoretiske).Yield: 26.9 g (78.6% of theory).
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Analogt opnåedes de følgende forbindelser: 6-(3-chlor-propoxy)-4-i sopropyl-4H-3,1-benzoxaz in-2-on ud fra 6-hydroxy-4-isopropyl-4H-3,l-benzoxazin-2-on og 3-brom-propylchlorid.Analogously, the following compounds were obtained: 6- (3-chloro-propoxy) -4-i-sopropyl-4H-3,1-benzoxazin-2-one from 6-hydroxy-4-isopropyl-4H-3,1-benzoxazine -2-one and 3-bromo-propyl chloride.
5 Smp.: 104-105°C.Mp: 104-105 ° C.
Udbytte: 68,0% af det teoretiske.Yield: 68.0% of theory.
6-(3-chlor-propoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 103-brom-propylchlorid.6- (3-Chloro-propoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 103-bromo-propyl chloride.
Smp.: 137-138°C.Mp: 137-138 ° C.
Udbytte: 71,6% af det teoretiske.Yield: 71.6% of theory.
6-(6-brom-hexyloxy) -4,4-dimethyl-4H-3,1-benzoxaz in-2-on 15 ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 1,6-dibromhexan.6- (6-Bromohexyloxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazine-2 -one and 1,6-dibromohexane.
Smp.: 125-126°C.Mp: 125-126 ° C.
Udbytte: 59,2% af det teoretiske.Yield: 59.2% of theory.
20 6-(2-chlor-ethyl)-4,4-dimethyl-4H-3,l-benzoxazin-2-on ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og benzensulfonsyre-(2-chlor-ethyl)-ester.6- (2-Chloroethyl) -4,4-dimethyl-4H-3,1-benzoxazin-2-one from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazine-2-one one and benzenesulfonic acid (2-chloroethyl) ester.
Smp.: 128-129°C.Mp: 128-129 ° C.
Udbytte: 34,4% af det teoretiske.Yield: 34.4% of theory.
2525
Eksempel EExample E
6-(4-Acetoxy-butoxy)-4H-3,1-benzoxazin-2-on.6- (4-Acetoxy-butoxy) -4H-3,1-benzoxazin-2-one.
102 g (0,62 mol) 6-hydroxy-4H-3,l-benzoxazin-2-on opløstes i 1 liter dimethylsulfoxid og tilsattes 227 30 g (1,64 mol) kaliumcarbonat og 166 g (0,73 mol) 4-acet-oxybutylbromid. Reaktionsblandingen omrørtes i 6 timer ved 50°C og tilsattes derefter isvand. Bundfaldet afsugedes, vaskedes med vand og tørredes.102 g (0.62 mole) of 6-hydroxy-4H-3,1-benzoxazin-2-one was dissolved in 1 liter of dimethyl sulfoxide and 227 30 g (1.64 mole) of potassium carbonate and 166 g (0.73 mole) were added. aceto-oxybutylbromid. The reaction mixture was stirred for 6 hours at 50 ° C and then ice water was added. The precipitate was aspirated, washed with water and dried.
Smp. 119-120°C.Mp. 119-120 ° C.
35 Udbytte: 142,8 g (82,7% af det teoretiske).Yield: 142.8 g (82.7% of theory).
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Analogt opnåedes de følgende forbindelser: 6-(4-acetoxy-butoxy)-4, 4-dimethyl-4H-3,l-benzoxazin-2-on olie; RF-værdi: 0,8 (kiselgelplade: chloroform/etha-5 nol = 9:1).Analogously, the following compounds were obtained: 6- (4-acetoxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one oil; RF value: 0.8 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 100% af det teoretiske.Yield: 100% of theory.
6- (4-acetoxy-butoxy)-4,4-di-n-hexyl-4H-3,1-benzoxazin-2-on olie; RF-værdi: 0,6 (kiselgelplade: chloroform/ace-10 tone = 9:1).6- (4-acetoxy-butoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one oil; RF value: 0.6 (silica gel plate: chloroform / ace-10 tone = 9: 1).
Udbytte: 100% af det teoretiske.Yield: 100% of theory.
6- (4-acetoxy-butoxy)-4,4-diphenyl-4H-3,1-benzoxazin-2-on; olie, RF-værdi: 0,55 (kiselgelplade: chloroform/ace-15 tone = 9:1).6- (4-acetoxy-butoxy) -4,4-diphenyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.55 (silica gel plate: chloroform / ace-tone = 9: 1).
Udbytte: 81% af det teoretiske.Yield: 81% of theory.
6- (4-acetoxy-butoxy)-4,4-dicyclohexyl-4H-3,1-benzoxa-zin-2-on.6- (4-acetoxy-butoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
20 Smp.: 177-178°C.Mp: 177-178 ° C.
Udbytte: 68,8% af det teoretiske.Yield: 68.8% of theory.
7- (4-acetoxy-butoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on; olie, RF-værdi: 0,5 (kiselgelplade:ethylenchlorid/- 25 ethanol = 9:1).7- (4-acetoxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.5 (silica gel plate: ethylene chloride / ethanol = 9: 1).
Udbytte: 100% af det teoretiske.Yield: 100% of theory.
8- (4-acetoxy-butoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on.8- (4-Acetoxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
30 Smp.: 154-158°C.Mp: 154-158 ° C.
Udbytte; 100% af det teoretiske.Yield; 100% of the theoretical.
6-(4-acetoxy-butoxy)-4,4-diethy1-4H-3,1-benzoxazin-2-on; olie, RF-værdi: 0,38 (kiselgelplade: 35 chloroform/ethanol = 19:1).6- (4-acetoxy-butoxy) -4,4-diethy1-4H-3,1-benzoxazin-2-one; oil, RF value: 0.38 (silica gel plate: 35 chloroform / ethanol = 19: 1).
Udbytte: 95% af det teoretiske.Yield: 95% of theory.
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6- (4-a eetoxy-butoxy) -4-methy1-4H-3,1 -benzoxaz in-2-on; olie, RF-værdi: 0,5 (kiselgelplade: chloroform/ethanol = 9:1).6- (4-aethoxy-butoxy) -4-methyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.5 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 98% af det teoretiske.Yield: 98% of theory.
5 6-(4-acetoxy-butoxy)-4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-on; olie, RF-værdi: 0,8 (kiselgelplade: chloroform/acetone = 9:1).6- (4-acetoxy-butoxy) -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one; oil, RF value: 0.8 (silica gel plate: chloroform / acetone = 9: 1).
Udbyte: 97% af det teoretiske.Yield: 97% of theory.
10 6- (4-acetoxy-butoxy)-4,4,8-trimethyl-4H-3,1-benzoxazin-2-on; olie, RF-værdi: 0,5 (kiselgelplade: ethylenchlo-rid/acetone = 9:1).6- (4-acetoxy-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.5 (silica gel plate: ethylene chloride / acetone = 9: 1).
Udbytte: 98% af det teoretiske.Yield: 98% of theory.
1515
Eksempel FExample F
6 - (4-Hydroxy-butoxy) -4H-3, l-benzoxazin-2-on.6- (4-Hydroxy-butoxy) -4H-3,1-benzoxazin-2-one.
Til en opløsning af 150 g (0,537 mol) 6-(4-acet-oxy-butoxy)-4H-3, l-benzoxazin-2-on i 500 ml methanol 20 dryppedes under omrøring ved 10 til 15°C en opløsning af 24 g (0,6 mol) natriumhydroxid i 100 ml vand. Efter 1 times efteromrøring ved stuetemperatur tilsattes først isvand og derefter 60 ml iseddikesyre. Det udfældede produkt sugedes af og omkrystalliseredes i vand.To a solution of 150 g (0.537 mol) of 6- (4-acetoxy-butoxy) -4H-3,1-benzoxazin-2-one in 500 ml of methanol was added dropwise with stirring at 10 to 15 ° C. 24 g (0.6 mole) of sodium hydroxide in 100 ml of water. After 1 hour of stirring at room temperature, ice water was first added and then 60 ml of glacial acetic acid. The precipitated product was suctioned off and recrystallized in water.
25 Smp.: 133-134°C.Mp: 133-134 ° C.
Udbytte: 61,5 g (48,4% af det teoretiske).Yield: 61.5 g (48.4% of theory).
Analogt opnåedes de følgende forbindelser: 6- (4-hydr oxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-30 on.Analogously, the following compounds were obtained: 6- (4-Hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazine-2-30 one.
Smp.: 124°C.Mp: 124 ° C.
Udbytte: 82,9% af det teoretiske.Yield: 82.9% of theory.
6- (4-hydroxy-butoxy) -4,4-diphenyl-4H-3, l-benzoxazin-2-35 on.6- (4-hydroxy-butoxy) -4,4-diphenyl-4H-3,1-benzoxazine-2-35 one.
Smp.: 188-189°C.Mp: 188-189 ° C.
Udbytte: 79% af det teoretiske.Yield: 79% of theory.
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6- (4-hydroxy-butoxy )-4,4-di-n-hexyl-4H-3,1-benzoxazin-2-on.6- (4-hydroxy-butoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Smp.: 105-107°C.Mp: 105-107 ° C.
Udbytte: 56% af det teoretiske.Yield: 56% of theory.
5 6- (4-hydroxy-butoxy) -4,4-dicyclohexyl-4H-3,1-benz-oxazin-2-on.6- (4-hydroxy-butoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Smp.; 233-234°C.m.p .; 233-234 ° C.
Udbytte: 77,6% af det teoretiske.Yield: 77.6% of theory.
10 7- (4-hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-on.7- (4-hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 105-106°C.Mp: 105-106 ° C.
Udbytte: 53,4% af det teoretiske.Yield: 53.4% of theory.
15 8- (4-hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-on.8- (4-hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 150-151°C.Mp: 150-151 ° C.
Udbytte: 73% af det teoretiske.Yield: 73% of theory.
20 6- (4-hydroxy-butoxy) -4,4-diethyl-4H-3, l-benzoxazin-2-on.6- (4-hydroxy-butoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Smp.: 126-127°C.Mp: 126-127 ° C.
Udbytte: 69,3% af det teoretiske.Yield: 69.3% of theory.
25 6- (4-hydroxy-butoxy) -4-methyl-4H-3, l-benzoxazin-2-on; olie, RF-værdi: 0,4 (kiselgelplade: chloroform/ethanol = 9:1).6- (4-hydroxy-butoxy) -4-methyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.4 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 61,6% af det teoretiske.Yield: 61.6% of theory.
30 6-(4-hydroxy-butoxy)-4,4-dimethyl-7-nitro-4H-3,1-benz-oxazin-2-on.6- (4-hydroxy-butoxy) -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.
Smp.: 140-141 °C.Mp: 140-141 ° C.
Udbytte: 37,8% af det teoretiske.Yield: 37.8% of theory.
35 DK 164860 6 43 6-(4-hydroxy-butoxy)-4,4,8-trimethyl-4H-3,1-benzoxazin-2-on.6- (4-hydroxy-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 128-129°C.Mp: 128-129 ° C.
Udbyttes 64,2% af det teoretiske.Yield 64.2% of theory.
55
Eksempel GExample G
6-(4-Chlor-butoxy)-4H-3,l-benzoxazin-2-on.6- (4-Chloro-butoxy) -4H-3, l-benzoxazin-2-one.
Til 300 ml thionylchlorid sattes under omrøring ved stuetemperatur 60 g (0,253 mol) 6-(4-hydroxy-but-10 oxy)-4H-3,l-benzoxazin-2-on og 5 ml pyridin. Efter 2 timers tilbagesvalingskogning afdestilleredes det overskydende thionylchlorid i en rotationsfordamper, resten optoges i chloroform og omrørtes sammen med de samme rumfang isvand i 30 minutter. Derefter isoleredes chlo-15 roformfasen, vaskedes yderligere to gange med vand, tørredes med natriumsulfat, og chloroformen afdestilleredes. Resten omkrystalliseredes i toluen/diisopropylether = 3:1.To 300 ml of thionyl chloride was added with stirring at room temperature 60 g (0.253 mol) of 6- (4-hydroxy-butoxy) -4H-3,1-benzoxazin-2-one and 5 ml of pyridine. After 2 hours of reflux, the excess thionyl chloride was distilled off in a rotary evaporator, the residue was taken up in chloroform and stirred with the same volume of ice water for 30 minutes. Then the chloroform phase was isolated, washed two more times with water, dried over sodium sulfate and the chloroform distilled off. The residue was recrystallized from toluene / diisopropyl ether = 3: 1.
Smp.: 127-128°C.Mp: 127-128 ° C.
20 Udbytte; 53 g (81,9% af det teoretiske).Yield; 53 g (81.9% of theory).
Analogt opnåedes de følgende forbindelser: 6-(4-chlor-butoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Analogously, the following compounds were obtained: 6- (4-chloro-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 138-139°C.Mp: 138-139 ° C.
25 Udbytte: 75,7% af det teoretiske.Yield: 75.7% of theory.
6-(4-chlor-butoxy)-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on; olie, RF-værdi: 0,65 (kiselgelplade; chloroform/ace-tone = 9:1).6- (4-chloro-butoxy) -4,4-di-n-hexyl-4H-3, l-benzoxazin-2-one; oil, RF value: 0.65 (silica gel plate; chloroform / ace tone = 9: 1).
30 Udbytte: 100% af det teoretiske.Yield: 100% of theory.
6-(4-chlor-butoxy)-4,4-diphenyl-4H-3,l-benzoxazin-2-on olie, RF-værdi: 0,38 (kiselgelplade? cyclohexan/eddike-syreethylester = 9:1).6- (4-chloro-butoxy) -4,4-diphenyl-4H-3,1-benzoxazin-2-one oil, RF value: 0.38 (silica gel plate cyclohexane / acetic acid ethyl ester = 9: 1).
3535
Udbytte: 28,7% af det teoretiske.Yield: 28.7% of theory.
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6- (4-chlor—butoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-on.6- (4-chloro-butoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Smp.s 231-232°C.Mp 231-232 ° C.
Udbytte: 72,8% af det teoretiske.Yield: 72.8% of theory.
5 6- (4-chlor-butoxy )-4, 4-diethyl-4H-3, l-benzoxazin-2-on.6- (4-Chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Smp.: 90-92°C.Mp: 90-92 ° C.
Udbytte: 99,4% af det teoretiske.Yield: 99.4% of theory.
10 6-(4-chlor-butoxy)-4-methyl-4H-3, l-benzoxazin-2-on; olie, RP-værdi: 0,8 (kiselgelplade: chloroform/ethanol = 9:1).6- (4-chloro-butoxy) -4-methyl-4H-3,1-benzoxazin-2-one; oil, RP value: 0.8 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 32,1% af det teoretiske.Yield: 32.1% of theory.
15 8-(4-chlor-butoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on.8- (4-Chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Snip.: 155-156°C.Snip: 155-156 ° C.
Udbytte: 93,8% af det teoretiske.Yield: 93.8% of theory.
6- (4-chlor-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-20 2-on.6- (4-chloro-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 149-150°C.Mp: 149-150 ° C.
Udbytte: 95,6% af det teoretiske.Yield: 95.6% of theory.
Eksempel HExample H
25 7- (4-Methansulfonyloxy-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on.7- (4-Methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5,3 g (0,02 mol) 7-(4-hydroxy-butoxy)-4,4-dime-thyl-4H-3,l-benzoxazin-2-on opløstes i 20 ml pyridin og tilsattes under omrøring ved 0 til 5°c dråbevis 4,6 g 30 (0,04 mol) methansulfonsyrechlorid. Efter 10 minutters efteromrøring tilsattes isvand/saltsyre, og blandingen ekstraheredes med chloroform. Efter vask af ekstrakterne med vand og tørring med natriumsulfat afdestilleredes opløsningsmidlet i vakuum. Den faste rest rørtes op med 35 diisopropylether, sugedes af og tørredes.5.3 g (0.02 mol) of 7- (4-hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 20 ml of pyridine and added with stirring at 0 to 5 ° C drop 4.6 g (0.04 mole) of methanesulfonic acid chloride. After 10 minutes of stirring, ice-water / hydrochloric acid was added and the mixture extracted with chloroform. After washing the extracts with water and drying with sodium sulfate, the solvent was distilled off in vacuo. The solid residue was stirred with 35 diisopropyl ether, suctioned off and dried.
Smp.: 134-136°C.Mp: 134-136 ° C.
Udbytte: 6,4 g (93,3% af det teoretiske).Yield: 6.4 g (93.3% of theory).
45 DK 16486U 845 DK 16486U 8
Analogt fremstilledes den følgende forbindelses 6- (4-methansulfonyloxy-butoxy )-4,4-dimethyl-7-nitro-4H-3,l-benzoxazin-2-on.Analogously, the following compound 6- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one was prepared.
Smp.: 149-151°C.Mp: 149-151 ° C.
5 Udbytte: 76,6% af det teoretiske.Yield: 76.6% of theory.
Eksempel IExample I
3-Methoxy-anthranilsyre-methylester.3-methoxy-anthranilic acid methyl ester.
133 g (0,63 mol) 3-methoxy-2-nitro-benzoesyre-10 methylester opløstes i 1000 ml toluen og hydrogeneredes i en autoklave ved stuetemperatur og 5 bar hydrogentryk i nærværelse af platin i løbet af 2 timer. Katalysatoren affiltreredes, blandingen tørredes med natriumsulfat, og toluenet afdestilleredes i vakuum.133 g (0.63 mol) of 3-methoxy-2-nitrobenzoic acid methyl ester was dissolved in 1000 ml of toluene and hydrogenated in an autoclave at room temperature and 5 bar hydrogen pressure in the presence of platinum over 2 hours. The catalyst was filtered off, the mixture dried with sodium sulfate and the toluene distilled off in vacuo.
15 Olie, RF-værdi 0,8 (kiselgelplade: chloroform/ acetone = 9:1).Oil, RF value 0.8 (silica gel plate: chloroform / acetone = 9: 1).
Udbytte: 110 g (96,4% af det teoretiske).Yield: 110 g (96.4% of theory).
På grund af dets relative instabilitet er det ik-20 ke hensigtsmæssigt at opbevare stoffet, men straks analogt med eksempel A at omsætte det videre.Because of its relative instability, it is not appropriate to store the substance, but immediately analogous to Example A to react further.
Eksempel JExample J
6-Methoxy-anthranilsyre-methylester-hydrochlorid.6-methoxy-anthranilic acid methyl ester hydrochloride.
25 a) 2-Cyano-3-methoxy-anilin.A) 2-Cyano-3-methoxy-aniline.
110 g (0,617 mol) 2-methoxy-6-nitro-benzonitril opløstes i 1 liter methanol og hydrogeneredes i nærværelse af 10%’ig palladiumcarbon ved stuetemperatur og 5 bar hydrogentryk indenfor 1 time i en autoklave. Kata-30 lysatoren affiltreredes, opløsningsmidlet afdestilleredes, og resten omkrystalliseredes i ethanol/diisopro-pylether.110 g (0.617 mol) of 2-methoxy-6-nitro-benzonitrile was dissolved in 1 liter of methanol and hydrogenated in the presence of 10% of palladium carbon at room temperature and 5 bar hydrogen pressure within 1 hour in an autoclave. The catalyst was filtered off, the solvent was distilled off and the residue was recrystallized from ethanol / diisopropyl ether.
Smp.: 142-143°C.Mp: 142-143 ° C.
Udbytte: 54,8 g (59,9% af det teoretiske).Yield: 54.8 g (59.9% of theory).
35 b) 6-Methoxy-anthranilsyre.B) 6-Methoxy-anthranilic acid.
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54 g (0,364 mol) af det ved a) fremstillede produkt opvarmedes sammen med 800 ml 25%'ig vandig opløsning af kaliumhydroxid i 16 timer under tilbagesvaling. Efter afkøling bragtes reaktionsopløsningen ved .tilsæt-5 ning af eddikesyre til pH = 6 og ekstraheredes flere gange hver gang med ½ liter eddikesyreethylester. De samlede ekstrakter tørredes med natriumsulfat og eddi-kesyreethylesteren afdestilleredes. Resten rensedes søjlechromatografisk (kiselgel, ethylenchlorid/acetone = 10 19:1). De samlede fraktioner reduceredes til tørhed.54 g (0.364 mol) of the product prepared by a) was heated together with 800 ml of 25% aqueous potassium hydroxide solution for 16 hours at reflux. After cooling, the reaction solution was brought to pH = 6 by the addition of acetic acid and extracted several times each with ½ liter of acetic acid ethyl ester. The combined extracts were dried over sodium sulfate and the acetic acid ethyl ester was distilled off. The residue was purified by column chromatography (silica gel, ethylene chloride / acetone = 19: 1). The total fractions were reduced to dryness.
Smp. 76-78°C.Mp. 76-78 ° C.
Udbytte: 37,5 g (61,7% af det teoretiske).Yield: 37.5 g (61.7% of theory).
c) 6-Methoxy-anthranilsure-methylester-hydrochlorid.c) 6-Methoxy-anthranilic acid methyl ester hydrochloride.
15 Den ved b) opnåede syre (37,5 g = 0,22 mol) opløstes i 500 ml methanol, og opløsningen tilførtes i 2 timer på koncentreret svovlsyre tørret hydrogenchlorid. Herved udfældedes en tyk krystalgrød, der tilsattes 500 ml ether, sugedes af og endiiu en gang vaskedes med 20 ether.The acid obtained at b) (37.5 g = 0.22 mol) was dissolved in 500 ml of methanol and the solution was added for 2 hours on concentrated sulfuric acid dried hydrogen chloride. This precipitated a thick crystal porridge added to 500 ml of ether, suctioned off and finally washed once with 20 ether.
Smp.: 209°C (sønderdeling).Mp: 209 ° C (dec.).
Udbytte: 36,5 g (75,2% af det teoretiske).Yield: 36.5 g (75.2% of theory).
Eksempel KExample K
2 5 4-Methoxy-anthranilsyre-methylester.2 5 4-Methoxy-anthranilic acid methyl ester.
a) 3-(Isonitroso-acetamido)-anisol.a) 3- (Isonitroso-acetamido) anisole.
1480 g (10,38 mol) natriumsulfat og 225 g (1,36 mol) chloralhydrat opløstes i 6 liter vand og opvarmedes til 50°C. Hertil sattes under omrøring en opløsning af 30 154 g (1,25 mol) m-anisidin i 750 ml vand og 125 ml koncentreret saltsyre. 5 Minutter senere tilsattes en opløsning af 275 g (3,96 mol) hydroxylaramoniumhydrochlorid i 1,25 liter vand og opvarmedes til 95°C. Under fortsat omrøring afkøledes til stuetemperatur, bundfaldet suge-35 des af, vaskedes med vand og tørredes. Smp.: 165-166°C.1480 g (10.38 mole) of sodium sulfate and 225 g (1.36 mole) of chlorohydrate were dissolved in 6 liters of water and heated to 50 ° C. To this was added, with stirring, a solution of 30 154 g (1.25 moles) of m-anisidine in 750 ml of water and 125 ml of concentrated hydrochloric acid. Five minutes later, a solution of 275 g (3.96 mole) of hydroxylaramonium hydrochloride in 1.25 liters of water was added and heated to 95 ° C. With continued stirring, it was cooled to room temperature, the precipitate was sucked off, washed with water and dried. Mp: 165-166 ° C.
Udbytte: 242,5 g (99,9% af det teoretiske).Yield: 242.5 g (99.9% of theory).
47 DK 164bbU b47 DK 164bbU b
Analogt fremstilledes de følgende forbindelser: 4-(Isonitroso-acetamido)-3-methyl-anisol.Analogously, the following compounds were prepared: 4- (Isonitroso-acetamido) -3-methyl-anisole.
Smp.: 166-167°C.Mp: 166-167 ° C.
Udbytte: 94,1% af det teoretiske.Yield: 94.1% of theory.
5 4-(Isonitroso-acetamido)-2-methyl-anisol.4- (Isonitroso-acetamido) -2-methyl-anisole.
Smp.: 169-171°C.Mp: 169-171 ° C.
Udbytte: 86,2% af det teoretiske.Yield: 86.2% of theory.
10 2-Chlor-4-(isonitroso-acetamido)-anisol.2-Chloro-4- (isonitroso-acetamido) anisole.
Smp.: 208°C.Mp: 208 ° C.
Udbytte: 91,6% af det teoretiske, b) 6-Methoxy-isatin.Yield: 91.6% of theory, b) 6-Methoxy-isatin.
15 Ved 60°C rørtes 140 g (0,72 mol) 3-(isonitroso- acetamido)-anisol ind i 720 g polyphosphorsyre. Herved opvarmedes blandingen til 100°C. Ved denne temperatur omrørtes der i yderligere 30 minutter, reaktionsblandingen afkøledes derefter og hældtes under omrøring til 4 20 liter 30°C varmt vand. Efter henstand natten over af-sugedes bundfaldet, vaskedes med vand og udkogtes med acetone/chloroform = 1:1. Opløsningen tørredes med natriumsulfat, og opløsningsmidlet afdestilleredes. Resten rørtes op med ethanol, sugedes af og tørredes ved 25 stuetemperatur.At 60 ° C, 140 g (0.72 mole) of 3- (isonitroso-acetamido) anisole was stirred into 720 g of polyphosphoric acid. The mixture was then heated to 100 ° C. At this temperature, it was stirred for a further 30 minutes, then the reaction mixture was cooled and poured under stirring to 4 20 liters of 30 ° C hot water. After standing overnight, the precipitate was suctioned off, washed with water and boiled with acetone / chloroform = 1: 1. The solution was dried over sodium sulfate and the solvent was distilled off. The residue was stirred with ethanol, suctioned off and dried at room temperature.
Smp.: 237-238°C.Mp: 237-238 ° C.
Udbytte: 84,2 g (65,9% af det teoretiske).Yield: 84.2 g (65.9% of theory).
Analogt fremstilledes de følgende forbindelser: 30 5-Methoxy-7-methyl-isatin.Analogously, the following compounds were prepared: 5-Methoxy-7-methyl-isatin.
Smp.: 265-266°C.Mp: 265-266 ° C.
Udbytte: 36% af det teoretiske.Yield: 36% of theory.
5-Methoxy-6-methyl-isatin.5-methoxy-6-methyl isatin.
35 Smp.: 254-256°C.Mp: 254-256 ° C.
Udbytte: 87,2% af det teoretiske.Yield: 87.2% of theory.
DK 164860BDK 164860B
48 6- Chlor-5-methoxy-isatin.48 6- Chloro-5-methoxy-isatin.
Smp.: 247°C.Mp: 247 ° C.
Udbytte: 33,2% af det teoretiske.Yield: 33.2% of theory.
5 c) 4-Methoxy-anthranilsyre-methylester.C) 4-Methoxy-anthranilic acid methyl ester.
158 g (0,89 mol) 6-methoxy-isatin suspenderedes i 1300 ml methanol og tilsattes en opløsning af 54 g (1,34 mol) natriumethylat i 500 ml methanol. Hertil dryppedes under omrøring 108 ml (1,07 mol) 30%'ig hydirogenperoxid 10 og omrørtes i yderligere 30 minutter. Kolbeindholdet reduceredes til det halve rumfang tilsattes vand og indstilledes med iseddikesyre til pH = 5-6. Efter ekstraktion med methylenchlorid afsugedes blandingen på kisel-gur, tørredes med natriumsulfat, og opløsningsmidlet 15 afdestilleredes. Resten omkrystalliseredes i petroleums-ether/cyclohexan = 2:1.158 g (0.89 mol) of 6-methoxy-isatin was suspended in 1300 ml of methanol and a solution of 54 g (1.34 mol) of sodium ethylate in 500 ml of methanol was added. To this, 108 ml (1.07 mole) of 30% hydirogen peroxide 10 was added with stirring and stirred for a further 30 minutes. The flask content was reduced to half the volume of water added and adjusted with glacial acetic acid to pH = 5-6. After extraction with methylene chloride, the mixture was suctioned on silica, dried over sodium sulfate, and the solvent was distilled off. The residue was recrystallized in petroleum ether / cyclohexane = 2: 1.
Smp.: 80-82°C.Mp: 80-82 ° C.
Udbytte: 109 g (67,7% af det teoretiske).Yield: 109 g (67.7% of theory).
Analogt fremstilledes de følgende forbindelser: 20 5-Methoxy-3-methyl-anthranilsyre-methylester.Analogously, the following compounds were prepared: 5-Methoxy-3-methyl-anthranilic acid methyl ester.
Smp.: 81-82°C.Mp: 81-82 ° C.
Udbytte: 59,6% af det teoretiske.Yield: 59.6% of theory.
5-Methoxy-4-methyl-anthranilsyre-methylester.5-methoxy-4-methyl-anthranilic acid methyl ester.
25 Smp.: 84-86°C.Mp: 84-86 ° C.
Udbytte: 82,2% af det teoretiske.Yield: 82.2% of theory.
Eksempel LExample L
8-Chlor-6-methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 7- chlor-6-methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on.8-Chloro-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 7-chloro-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazine-2 -on.
En opløsning af 79 g (0,38 mol) 6-methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on i 1000 ml chloroform tilsattes 56,68 g (0,42 mol) sulforylchlorid og omrørtes 35 i 6 timer ved 10-20°C. Efter henstand natten over tilsattes reaktionsblandingen en vandig natriumcarbonatop- 49A solution of 79 g (0.38 mol) of 6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one in 1000 ml of chloroform was added 56.68 g (0.42 mol) of sulforyl chloride and stirred. 35 for 6 hours at 10-20 ° C. After standing overnight, the reaction mixture was added an aqueous sodium carbonate solution 49
DK 164860 BDK 164860 B
løsning, den organiske fase isoleredes, vaskedes med vand, tørredes med natriumsulfat, og chloroformen afde-stilleredes. Resten opdeltes søjlechromatografisk i iso-merene (kiselgel, ethylenchlorid/acetone = 19:1). De 5 samledes fraktioner reduceredes til tørhed, og resten omkrystalliseredes i eddikesyreethylester/diisopro-pylether.solution, the organic phase was isolated, washed with water, dried over sodium sulfate and the chloroform was distilled off. The residue was partitioned column chromatographically into the isomers (silica gel, ethylene chloride / acetone = 19: 1). The 5 total fractions were reduced to dryness and the residue was recrystallized from acetic acid ethyl ester / diisopropyl ether.
1) 8-Chlor-6-methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2- 10 on.1) 8-Chloro-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 156-157°CMp: 156-157 ° C
Udbytte: 47,3 g (51,6% af det teoretiske).Yield: 47.3 g (51.6% of theory).
2) 7-Chlor-6-methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2- 15 on.2) 7-Chloro-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 165-167°C.Mp: 165-167 ° C.
Udbytte: 18,9 g (20,6% af det teoretiske).Yield: 18.9 g (20.6% of theory).
Eksempel MExample M
20 8-Brom-6-methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 7 -brom-6-methoxy-4,4-dimethyl-4H-3, l-benzoxazin-2-on.8-Bromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 7-bromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazine-2 -on.
82,7 g (0,4 mol) 6-methoxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on opløstes i 800 ml dioxan og tilsattes 25 ved stuetemperatur dråbevis 67,1 g (21,5 ml = 0,42 mol) brom. Efter 3 timers omrøring tilsattes yderligere 67,1 g brom og efter yderligere 3 timer en tredie gang brom 67,1 g. Omrøringen fortsattes natten over. Reaktionsblandingen tilsattes derefter isvand og natriumhydro-30 gensulfitopløsning og ekstraheredes med eddikesyreethyl-ester. Ekstrakten vaskedes med vand, tørredes med natriumsulfat, og eddikesyreethylesteren afdestilleredes. Resten opdeltes søjlechromatografisk i isomerene (kiselgel, ethylenchlorid/acetone = 60:1). De rene fraktioner 35 reduceredes og omkrystalliseredes i eddikesyreethyl-ester/diisopropylether.82.7 g (0.4 mole) of 6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 800 ml of dioxane and added dropwise 67.1 g (21.5) at room temperature. ml = 0.42 mol) of bromine. After 3 hours of stirring, an additional 67.1 g of bromine was added and after a further 3 hours a third of bromine 67.1 g of stirring was continued overnight. The reaction mixture was then added with ice water and sodium hydrogen sulfite solution and extracted with acetic acid ethyl ester. The extract was washed with water, dried over sodium sulfate and the acetic acid ethyl ester distilled off. The residue was column chromatographed into the isomers (silica gel, ethylene chloride / acetone = 60: 1). The pure fractions were reduced and recrystallized from acetic acid ethyl ester / diisopropyl ether.
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1) 8 -Brom-6 -methoxy-4,4-dimethyl-4H-3, l-benzoxazin-2-on.1) 8-Bromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp. 128-130°C (indeholdt stadig lidt 7,8-dibrom-6-methoxy-4,4-dimethyl-4H-3, l-benzoxazin-2-on).Mp. 128-130 ° C (still contained slightly 7,8-dibromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one).
Udbytte: 45 g (39,3% af det teoretiske).Yield: 45 g (39.3% of theory).
5 2) 7-Brom-6-methoxy-4,4-dimethyl-4H-3,1 -benzoxazin-2-on.2) 7-Bromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Smp.: 174-175°C.Mp: 174-175 ° C.
Udbytte: 33,7 g (29,5% af det teoretiske).Yield: 33.7 g (29.5% of theory).
10 Eksempel NExample N
6-Acetoxy-8-chlor-4H-3,l-benzoxazin-2-on.6-acetoxy-8-chloro-4H-3, l-benzoxazin-2-one.
14,5 g (0,07 mol) 6-acetoxy-4H-3,l-benzoxazin-2-on (fremstillet ud fra 6-hydroxy-4H-3,l-benzoxazin-2-on og acetanhydrid. Smp.: 173-175°C) opløstes i 150 ml is-15 eddikesyre, tilsattes 10,8 g (6,5 ml = 0,08 mol) sulfo-rylchlorid og omrørtes i 36 timer ved stuetemperatur. Efter tilsætning af 30 ml ether afkøledes blandingen til 0°c, bundfaldet afsugedes, vaskedes med ether og tørredes.14.5 g (0.07 mol) of 6-acetoxy-4H-3,1-benzoxazin-2-one (prepared from 6-hydroxy-4H-3,1-benzoxazin-2-one and acetanic anhydride. 173-175 ° C) was dissolved in 150 ml of glacial acetic acid, 10.8 g (6.5 ml = 0.08 mol) of sulforyl chloride was added and stirred for 36 hours at room temperature. After addition of 30 ml of ether, the mixture was cooled to 0 ° C, the precipitate was aspirated, washed with ether and dried.
20 Smp.: 204-205°C.Mp: 204-205 ° C.
Udbytte: 7,7 g (45,5% af det teoretiske).Yield: 7.7 g (45.5% of theory).
Eksempel OExample O
8-Chlor-6-hydroxy-4H-3,l-benzoxazin-2-on.8-Chloro-6-hydroxy-4H-3, l-benzoxazin-2-one.
25 7,6 g (31,4 mmol) 6-acetoxy-8-chlor-4H-3,l- benzoxazin-2-on suspenderedes i 50 ml methanol og tilsattes under omrøring 20 ml (40 mmol) 2 n natronlud. Den straks opståede klare opløsning omrørtes i yderligere 10 minutter ved stuetemperatur, tilsattes vand og indstil-30 ledes surt med eddikesyre. Bundfaldet sugedes af og omkrystalliseredes i isopropanol.7.6 g (31.4 mmol) of 6-acetoxy-8-chloro-4H-3,1-benzoxazin-2-one was suspended in 50 ml of methanol and 20 ml (40 mmol) of 2 n sodium hydroxide solution was added with stirring. The clear solution immediately obtained was stirred for an additional 10 minutes at room temperature, water was added and acidified with acetic acid. The precipitate was sucked off and recrystallized from isopropanol.
Smp.: 250°C (sønderdeling).Mp: 250 ° C (dec.).
Udbytte: 3,3 g (52,7% af det teoretiske).Yield: 3.3 g (52.7% of theory).
LMV IDH-OOU DLMV IDH-OOU D
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Fremstilling af slutprodukter:Manufacture of end products:
Eksempel 1 6-[4-(4-Brom-phenylmercapto)-butoxy]-4,4-dimethyl-4H-5 3,l-benzoxazin-2-on.Example 1 6- [4- (4-Bromo-phenylmercapto) -butoxy] -4,4-dimethyl-4H-5,1-benzoxazin-2-one.
6,23 g (0,033 mol) 4-bromthiophenol og 8,28 g (0,06 mol) kaliumcarbonat omrørtes i 100 ml på molekyl-sigte tørret dimethylsulfoxid under nitrogenatmosfære ved stuetemperatur i 15 minutter og tilsattes derefter 10 8,51 g (0,03 mol) 6-(4-chlorbutoxy)-4,4-dimethyl-4H- 3,l-benzoxazin-2-on. Efter 1 times omrøring ved stuetemperatur tilsattes portionsvis vand, indtil der fremkom en tyk krystalgrød. Blandingen sugedes af, tørredes og onikrystalliseredes i eddikesyreethylester/diisopro-15 pylether.6.23 g (0.033 mol) of 4-bromothiophenol and 8.28 g (0.06 mol) of potassium carbonate were stirred in 100 ml of molecular sieve dried dimethyl sulfoxide under nitrogen atmosphere at room temperature for 15 minutes and then 8.51 g (0 (Mole) 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one. After stirring for 1 hour at room temperature, portion water was added until a thick crystal porridge was obtained. The mixture was suction dried, dried and unicrystallized in acetic acid ethyl ester / diisopropyl ether.
Smp.: 151-152°C.Mp: 151-152 ° C.
Udbytte: 9,2 g (70,3% af det teoretiske).Yield: 9.2 g (70.3% of theory).
Eksempel 2 20 6-[4-(4-Brom-3-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 2 6- [4- (4-Bromo-3-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
9,2 g (0,02 mol) 6-[4-(4-brom-3-methyl-phenylmer-capto) -butoxy ]-4,4-dimethyl-4H-3, l-benzoxazin-2-on op løstes i 100 ml iseddikesyre og tilsattes 2 ml (0,02 25 mol) 30%'ig hydrogenperoxid. Blandingen omrørtes i 3 timer ved stuetemperatur, hældtes på 400 ml vand og eks-traheredes 3 gange med eddikesyreethylester. Den organiske fase vaskedes med vand, tørredes med natriumsul-• fat, og eddikesyreethylesteren afdestilleredes. Den fa-30 ste rest omkrystalliseredes i eddikesyreethylester/di-isopropylether.9.2 g (0.02 mol) of 6- [4- (4-bromo-3-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one Dissolve in 100 ml glacial acetic acid and add 2 ml (0.02 mol) 30% hydrogen peroxide. The mixture was stirred for 3 hours at room temperature, poured into 400 ml of water and extracted 3 times with acetic acid ethyl ester. The organic phase was washed with water, dried over sodium sulfate and the acetic acid ethyl ester was distilled off. The first residue was recrystallized from acetic acid ethyl ester / di-isopropyl ether.
Smp.: 133-134°C.Mp: 133-134 ° C.
Udbytte: 8,1 g (85,2% af det teoretiske).Yield: 8.1 g (85.2% of theory).
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Eksempel 3 4,4-Dimethyl-6-[4-(2-pyridylsulfonyl)-butoxy]-4H-3,1-benzoxazin-2-on.Example 3 4,4-Dimethyl-6- [4- (2-pyridylsulfonyl) -butoxy] -4H-3,1-benzoxazin-2-one.
3,58 g (0,01 mol) 4,4-dimethyl-6-[4-(2-pyridyl-5 mercapto)-butoxy]-4H-3,l7benzoxazin-2-on opløstes i 60 ml myresyre og tilsattes 2,5 ml (0,025 mol) 30%'ig hy-drogenperoxid. Efter 3 timers omrøring ved stuetemperatur fortyndedes portionsvis med vand, ekstraberedes med eddikesyreethylester, den organiske fase tørredes med 10 natriumsulfat, og eddikesyreethylesteren afdestilleredes. Til rensning chromatograferedes blandingen på en kiselgelsøjle (0,05 til 0,2 mm partikelstørrelse) med en blanding af chloroform/ethanol (40:1), og de samlede fraktioner omkrystalliseredes efter afdestillation af 15 elueringsblandingen i eddikesyreethylester.3.58 g (0.01 mole) of 4,4-dimethyl-6- [4- (2-pyridyl-5-mercapto) -butoxy] -4H-3,7-benzoxazin-2-one was dissolved in 60 ml of formic acid and added 2 5 ml (0.025 mol) of 30% hydrogen peroxide. After stirring for 3 hours at room temperature, portions were diluted with water, extracted with acetic acid ethyl ester, the organic phase was dried over sodium sulfate and the acetic acid ethyl ester was distilled off. For purification, the mixture was chromatographed on a silica gel column (0.05 to 0.2 mm particle size) with a chloroform / ethanol (40: 1) mixture and the combined fractions were recrystallized after distilling off the elution mixture in acetic acid ethyl ester.
Smp. 142-143°C.Mp. 142-143 ° C.
Udbytte; 2,1 g (53,8% af det teoretiske).Yield; 2.1 g (53.8% of theory).
Eksempel 4 20 6-[4-(3,4-Dichlor-phenylsulfinyl)butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 4 6- [4- (3,4-Dichloro-phenylsulfinyl) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
En opløsning af 1,9 g (0,01 mol) 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4,1 g (0,0125 mol) 4-(3,4-dichlor-phenyl-sulfinyl)-butylbromid (smp.: 25 63-64°C) i 40 ml dimethylsulfoxid tilsattes 3,5 g (0,025 mol) kaliumcarbonat og omrørtes i 3 timer ved 40°C. Efter afkøling tilsattes rigeligt isvand og eks-traheredes med chloroform. Ekstrakten vaskedes med vand, tørredes med natriumsulfat, og chloroformen afdestille-30 redes. Resten omkrystalliseredes i isopropanol/diisopro-pylether.A solution of 1.9 g (0.01 mole) of 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4.1 g (0.0125 mole) of 4- (3, 4-Dichloro-phenyl-sulfinyl) -butyl bromide (m.p. 25 63-64 ° C) in 40 ml of dimethyl sulfoxide was added 3.5 g (0.025 mol) of potassium carbonate and stirred for 3 hours at 40 ° C. After cooling, ample ice water was added and extracted with chloroform. The extract was washed with water, dried over sodium sulfate and the chloroform distilled off. The residue was recrystallized from isopropanol / diisopropyl ether.
Smp.: 138°C.Mp: 138 ° C.
Udbytte: 1,9 g (43% af det teoretiske).Yield: 1.9 g (43% of theory).
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Eksempel 5 6- (4-Phenylmercapto-butoxy) -4H-3, l-benzoxazin-2-on.Example 5 6- (4-Phenylmercapto-butoxy) -4H-3,1-benzoxazin-2-one.
Til en ethanolisk natriumethylatopløsning, fremstillet ud fra 150 ml ethanol og 0,92 g (9,04 mol) na-5 trium, sattes 4,95 g (0,03 mol) 6-hydroxy-4H-3,l-benz-oxazin-2-on, og blandingen opvarmedes til tilbagesvaling. Den varme blanding tilsattes 10 g (0,04 mol) 4-phenylmercapto-butylbromid fremstillet ud fra thio-phenol og overskud af 1,4-dibrorabutan Kpo,03 mb = 10 95-104°C) og opvarraedes i yderligere 2 timer til tilbagesvaling. Den afkølede reaktionsopløsning hældtes til isvand og ekstraheredes med eddikesyreethylester. Ekstrakten vaskedes med vand, tørredes med natriumsulfat og eddikesyreethy lesteren af destilleredes i vakkum.To an ethanolic sodium ethylate solution prepared from 150 ml of ethanol and 0.92 g (9.04 mol) of sodium was added 4.95 g (0.03 mol) of 6-hydroxy-4H-3,1-benzene. oxazin-2-one and the mixture was heated to reflux. The hot mixture was added 10 g (0.04 mole) of 4-phenylmercapto-butyl bromide prepared from thio-phenol and excess 1,4-dibrorabutane (Kpo, 03 mb = 10 95-104 ° C) and stored for an additional 2 hours to reflux. The cooled reaction solution was poured into ice water and extracted with acetic acid ethyl ester. The extract was washed with water, dried over sodium sulfate and the acetic acid ethyl ester distilled off in vacuo.
15 Resten omkrystalliseredes i cyclohexan/eddikesyreethylester.The residue was recrystallized from cyclohexane / acetic acid ethyl ester.
Smp.: 96-97°C.Mp: 96-97 ° C.
Udbytte: 51,7% af det teoretiske.Yield: 51.7% of theory.
20 Eksempel 6 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 6 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
En opløsning af 32,65 g (0,074 mol) 6-[4-(3,4-dichlor-phenylsulf inyl) -butoxy ]-4,4-dimethyl-4H-3,1-25 benzoxazin-2-on i 300 ml dimethyl formamid tilsattes 66,6 g (0,35 mol) p-toluensulfonsyremonohydrat og 42,9 g (0,15 mol) O-mes ity lensul f ony 1-acethydroxamsyre-ethyl-ester og omrørtes i 30 timer ved stuetemperatur. Efter tilsætning af isvand ekstraheredes opløsningen med eddi-30 kesyreethylester, eddikesyreethylesterfasen vaskedes med vand, tørredes med natriumsulfat, og eddikesyreethyl-esteren afdestilleredes i vakuum. Resten opløstes i 200 ml methanol, og opløsningen tilsattes så meget 2 n natronlud, at den reagerede alkalisk. Ved tilsætning af 35 vand udfældedes reaktionsproduktet, ekstraheredes med eddikesyreethylester, ekstrakten vaskedes med vand og 54 ·A solution of 32.65 g (0.074 mol) of 6- [4- (3,4-dichloro-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one in 300 To dimethyl formamide, 66.6 g (0.35 mole) of p-toluenesulfonic acid monohydrate and 42.9 g (0.15 mole) of O-mesylene sulphonyl 1-acethydroxamic acid ethyl ester were added and stirred for 30 hours at room temperature. After adding ice water, the solution was extracted with acetic acid ethyl ester, the acetic acid ethyl ester phase washed with water, dried over sodium sulfate and the acetic acid ethyl ester distilled off in vacuo. The residue was dissolved in 200 ml of methanol and the solution was added with so much 2 n sodium hydroxide solution that it reacted alkaline. Upon addition of 35 water, the reaction product was precipitated, extracted with acetic acid ethyl ester, the extract washed with water and 54
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tørredes med natriumsulfat. Den efter afdestillation af eddikesyreethylesteren tilbageblevne rest omkrystalliseredes i eddikesyreethylester/diisopropylether.dried over sodium sulfate. The residue remaining after distillation of the acetic acid ethyl ester was recrystallized in acetic acid ethyl ester / diisopropyl ether.
Smp.: 166-167°C.Mp: 166-167 ° C.
5 Udbytte: 28,3 g (83,8% af det teoretiske).Yield: 28.3 g (83.8% of theory).
Eksempel 7 6-[4-(2-Pyridylsulfonyl) -butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on.Example 7 6- [4- (2-Pyridylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
10 3,58 g (0,01 mol) 6-[4-(2-pyridylmercapto)-but- oxy]-4,4 -dimethyl-4H-3,l-benzoxazin-2-on opløstes i 100 ml chloroform og tilsattes under omrøring 4,3 g (0,025 mol) m-chlor-perbenzoesyre. Efter 2 timers omrøring tilsattes yderligere 2 g m-chlor-perbenzoesyre, og blandin-15 gen henstilledes natten over. Chloroformfasen udrystedes med vand, den organiske fase tørredes med natriumsulfat, og chloroformen afdestilleredes. Den uensartede rest rensedes søjlechromatografisk (kiselgel; kornstørrelse: 0,05 til 0,2 mm, chloroform s ethanol = 40:1). De samlede 20 fraktioner reduceredes, og resten blev udrevet med eddi-kesyreethylester/ether. De således opnåede krystaller sugedes af og tørredes ved 50°C.3.58 g (0.01 mole) of 6- [4- (2-pyridylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 100 ml of chloroform and 4.3 g (0.025 mole) of m-chloro-perbenzoic acid were added with stirring. After 2 hours of stirring, an additional 2 g of m-chloro-perbenzoic acid was added and the mixture was allowed to stand overnight. The chloroform phase is shaken with water, the organic phase is dried over sodium sulfate and the chloroform is distilled off. The uniform residue was purified column chromatographically (silica gel; grain size: 0.05 to 0.2 mm, chloroform s ethanol = 40: 1). The total 20 fractions were reduced and the residue was triturated with acetic acid ethyl ester / ether. The crystals thus obtained were sucked off and dried at 50 ° C.
Smp.: 90-91°C.Mp: 90-91 ° C.
Udbytte: 1,0 g (26,7% af det teoretiske).Yield: 1.0 g (26.7% of theory).
2525
Eksempel 8 6 - [ 4- (3,4-Dichlor-phenylsulf inyl) -butoxy ] -4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 8 6 - [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
2,14 g (0,005 mol) 6-[4-(3,4-dichlor-phenylmer-30 capto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on opløstes i 50 ml methanol, tilsattes en opløsning af 1,3 g (0,06 mol) natriummetaperiodat i 10 ml vand og omrørtes i 2 timer ved stuetemperatur. Derefter opvarmedes der i yderligere 3 timer til tilbagesvaling, reaktionsblan-35 dingens rumfang reduceredes til ca. 3/4 og omrørtes med vand. Den udskilte olie isoleredes ved afdekantering 552.14 g (0.005 mole) of 6- [4- (3,4-dichloro-phenylmer-capto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 50 ml methanol, a solution of 1.3 g (0.06 mole) of sodium metaperiodate in 10 ml of water was added and stirred for 2 hours at room temperature. Then, for a further 3 hours to reflux, the volume of the reaction mixture was reduced to ca. 3/4 and stirred with water. The separated oil was isolated by decanting 55
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fra opløsningsmidlet og optoges i varm isopropanol/di-isopropylether, Ved afkøling udfældedes krystaller med smeltepunkt 138-139°C.from the solvent and taken up in hot isopropanol / di-isopropyl ether. On cooling, crystals of m.p. 138-139 ° C were precipitated.
Udbytte; 1,6 g (72,4% af det teoretiske).Yield; 1.6 g (72.4% of theory).
55
Eksempel 9 6- [4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 9 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Til en opløsning af 3,2 g (0,0075 mol) 6-[4-3,4-10 dichlorphenylmercapto)-butoxy]-4,4-dimethyl-4H-3,1- benzoxazin-2-on i 50 ml methylenchlorid dryppedes ved -70°C en opløsning af 1 g (0,0085 mol) sulfurylchlorid i 5 ml methylenchlorid under omrøring, og efter afsluttet tilsætning fortsattes omrøringen ved -70°C i yderligere 15 15 timer. Efter opvarmning til stuetemperatur tilsattes under kraftig omrøring vandig sodaopløsning, den organiske fase isoleredes fra den vandige, den vaskedes med vand og tørredes med natriumsulfat. Den efter afdestillation af methylenchloridet tilbageblevne rest omkry-20 stalliseredes i isopropanol/diisopropylether.To a solution of 3.2 g (0.0075 mol) of 6- [4-3,4-10 dichlorophenylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one in 50 ml methylene chloride was dropped at -70 ° C a solution of 1 g (0.0085 mole) of sulfuryl chloride in 5 ml of methylene chloride with stirring and after completion of the stirring was continued at -70 ° C for a further 15 hours. After warming to room temperature, aqueous soda solution was added with vigorous stirring, the organic phase was isolated from the aqueous, washed with water and dried over sodium sulfate. The residue remaining after distillation of the methylene chloride was recrystallized from isopropanol / diisopropyl ether.
Smp.: 138-139°C.Mp: 138-139 ° C.
Udbytte: 2,1 g (63,3% af det teoretiske).Yield: 2.1 g (63.3% of theory).
Eksempel 10 25 6-[4- (3,4-Dichlor-phenylsulf inyl) -butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on.Example 10 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Til en opløsning af 2,13 g (0,005 mol) 6-[4-(3,4-dichlor-pheny lmercapto) -butoxy ] -4,4-dimethyl-4H- 3,l-benzoxazin-2-on i 50 ml methanol sattes under 30 omrøring lidt efter lidt 1 g (0,0056 mol) N-brom-suc-cinimid. Efter 24 timers reaktionstid tilsattes 500 ml 80°C varmt vand, og bundfaldet afsugedes efter 2 timers omrøring. Ved omkrystallisation i isopropanol/diiso-propylether opnåedes krystaller med smeltepunkt 35 136-139°C.To a solution of 2.13 g (0.005 mol) of 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one in 50 ml of methanol was added little by little under 1 g (0.0056 mol) of N-bromosuccinimide. After 24 hours reaction time, 500 ml of 80 ° C hot water was added and the precipitate was aspirated after 2 hours of stirring. By recrystallization in isopropanol / diisopropyl ether crystals of melting point 35 136-139 ° C were obtained.
Udbytte: 1,55 g (70,1% af det teoretiske).Yield: 1.55 g (70.1% of theory).
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Eksempel 11 6- [4- (3,4-Dichlor-phenylsulf inyl) -butoxy ]-l, 4,4-tri-methyl-4H-3,l-benzoxazin-2-on.Example 11 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -1,4,4-trimethyl-4H-3,1-benzoxazin-2-one.
5 En opløsning af 1,1 g (0,0025 mol) 6-[4-(3,4- dicblor-phenylsulf inyl) -butoxy ]-4,4-dimethyl-4H-3,1-benzoxazin-2-on og 1 ml methyliodid i 30 ml methylen-chlorid tilsattes 30 ml 2 n natronlud (0,06 mol) og en spatelspids tetrabutylammonium-hydrogensulfat og 10 omrørtet i 18 timer ved stuetemperatur. Den organiske fase isoleredes, vaskedes to gange med vand, tørredes med natriumsulfat, og methylenchloridet afdestilleredes. Resten rensedes søjlechromatografisk (kiselgel, chloro-form/acetone = 40:1). De samlede fraktioner reducere-15 des, resten omrørtes med diisopropylether, krystalgrøden sugedes af og tørredes.A solution of 1.1 g (0.0025 mol) of 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 1 ml of methyl iodide in 30 ml of methylene chloride were added 30 ml of 2 n sodium hydroxide (0.06 mol) and a spatula tip tetrabutylammonium hydrogen sulfate and stirred for 18 hours at room temperature. The organic phase was isolated, washed twice with water, dried over sodium sulfate and the methylene chloride distilled off. The residue was purified by column chromatography (silica gel, chloroform / acetone = 40: 1). The combined fractions were reduced, the residue was stirred with diisopropyl ether, the crystal crop was sucked off and dried.
Smp.s 90-92°C.Mp 90-92 ° C.
Udbytte: 0,31 g (27,3% af det teoretiske).Yield: 0.31 g (27.3% of theory).
20 Eksempel 12 6-[4-(3,4-Dichlor-N-methansulfonyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,1 -benzoxaz in-2-on.Example 12 6- [4- (3,4-Dichloro-N-methanesulfonyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
2,3 g (0,005 mol) 6-[4-(3,4-dichlor-phenylsulf-oximino) -butoxy ] -4,4-dimethyl-4H-3, l-benzoxazin-2-on 25 opløstes i 50 ml chloroform og tilsattes 0,5 ml pyridin.2.3 g (0.005 mol) of 6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 50 ml chloroform and 0.5 ml of pyridine was added.
Til den denne opløsning sattes 1,2 g (0,01 mol) methan-sulfonylchlorid, og den omrørtes i 20 timer ved stuetemperatur. Chloroformfasen vaskedes flere gange med vand, tørredes med natriumsulfat, og chloroformen afdestille-30 redes. Resten rensedes søjlechromatografisk (kiselgel, chloroform/ethanol - 30:1). De samlede fraktioner reduceredes, og resten oxrikrystalliseredes i butanol/dimethyl formamid.To this solution was added 1.2 g (0.01 mole) of methanesulfonyl chloride and stirred for 20 hours at room temperature. The chloroform phase was washed several times with water, dried over sodium sulfate and the chloroform distilled off. The residue was purified by column chromatography (silica gel, chloroform / ethanol - 30: 1). The combined fractions were reduced and the residue was oxygen crystallized in butanol / dimethyl formamide.
Smp.: 198-200°C.Mp: 198-200 ° C.
35 Udbytte: 2,4 g (89,6% af det teoretiske).Yield: 2.4 g (89.6% of theory).
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Eksempel 13 6-[4-(3,4-Dimethoxy-phenylmercapto)-butoxy]-4,4-di-methyl-4H-3, l-benzoxazin-2-on'.Example 13 6- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6—(4 — 5 chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dimethoxy-thiophenol.Prepared analogously to Example 1 from 6- (4-5 chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.
Smeltepunkt: 140-142°C.Melting point: 140-142 ° C.
Udbytte: 65,9% af det teoretiske.Yield: 65.9% of theory.
Eksempel 14 10 6-[4-(4-Methoxy-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 14 6- [4- (4-Methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-methoxy-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-methoxy-thiophenol.
15 Smeltepunkt: 92-94°C.Melting point: 92-94 ° C.
Udbytte: 55,5% af det teoretiske.Yield: 55.5% of theory.
Eksempel 15 6-[4-(4-Hydroxy-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 15 6- [4- (4-Hydroxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6—(4— chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-hydroxy-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-hydroxythiophenol.
Smeltepunkt: 152-154°C.Melting point: 152-154 ° C.
Udbytte: 92,8% af det teoretiske.Yield: 92.8% of theory.
25 Eksempel 16 6-[4-(4-Biphenylylmercapto)-butoxy]-4,4-dimethyl-4H- 3,l-benzoxazin-2-on.Example 16 6- [4- (4-Biphenylyl mercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 4-phenyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4-phenylthiophenol.
Smeltepunkt: 120-122°C.Melting point: 120-122 ° C.
Udbytte: 87,2% af det teoretiske.Yield: 87.2% of theory.
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Eksempel 17 6- [4-(3-Methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 17 6- [4- (3-Methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3-methoxy-thiophenol.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3-methoxy-thiophenol.
Smeltepunkt; 115-116°C.Melting point; 115-116 ° C.
Udbytte; 79,6% af det teoretiske.Yield; 79.6% of theory.
Eksempel 18 10 6- [4- (3-Methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4 H-3,1-benzoxaz in-2-on.Example 18 6- [4- (3-Methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3-methyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3-methylthiophenol.
15 Smeltepunkt; 103-105°C.Melting point; 103-105 ° C.
Udbytte; 80,8% af det teoretiske.Yield; 80.8% of theory.
Eksempel 19 6-[4-(3,5-Di-tert.butyl-4-hydroxy-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 19 6- [4- (3,5-Di-tert.butyl-4-hydroxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,5-di-tert.butyl-4-hydroxy-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,5-di-tert.butyl-4-hydroxythiophenol.
Smeltepunkt: 86-87°C.Melting point: 86-87 ° C.
Udbytte: 76,2% af det teoretiske.Yield: 76.2% of theory.
25 Eksempel 20 6-[4-(4-Amino-3,5-dibrom-phenylmércapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 20 6- [4- (4-Amino-3,5-dibromo-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 4-amino-3,5-dibrom-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4-amino-3,5-dibromo-thiophenol.
Smeltepunkt: 152-155°C.Melting point: 152-155 ° C.
Udbytte: 85,5% af det teoretiske.Yield: 85.5% of theory.
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Eksempel 21 6-(4-n-Octylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 21 6- (4-n-Octylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on og n-octylmercaptan. Olie, RF-værdi: 0,8 (kiselgelpla-de; chlorform/acetone = 9:1).Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and n-octylmercaptan. Oil, RF value: 0.8 (silica gel plate; chloroform / acetone = 9: 1).
Udbytte: 96,1% af det teoretiske.Yield: 96.1% of theory.
C22H35N03S (393,59) 10 Beregnet: C 67,14 H 8,96 N 3,56 S 8,15C22H35NO3S (393.59) Calculated: C 67.14 H 8.96 N 3.56 S 8.15
Fundet : 67,31 9,00 3,57 8,25Found: 67.31 9.00 3.57 8.25
Eksempel 22 6-(4-Cyclohexylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on.Example 22 6- (4-Cyclohexylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
15 Fremstillet analogt med eksempel 1 ud fra 6- (4-chlorbutoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on og cyclohexylmercaptan.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and cyclohexylmercaptan.
Smeltepunkt: 105-107°C.Melting point: 105-107 ° C.
Udbytte: 82,5% af det teoretiske.Yield: 82.5% of theory.
20 Eksempel 23 6-[4-(4-Methyl-phenylmercapto)-butoxy]-4,4-di-n-hexyl-4h-3,l-benzoxazin-2-on.Example 23 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4h-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on 25 og 4-methyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one 25 and 4-methyl-thiophenol.
Smeltepunkt: 76-78°C.Melting point: 76-78 ° C.
Udbytte: 78,1% af det teoretiske.Yield: 78.1% of theory.
Eksempel 24 6-[4-(4-Cyclohexyl-phenylmercapto)-butoxy]-4,4-di-n-30 hexyl-4H-3,l-benzoxazin-2-on.Example 24 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on (olie, RF-værdi: 0,7; kiselgelplade; chlorform)acetone = 19:1) og 4-cyclohexyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one (oil, RF: 0.7; silica gel plate; chloroform) ) acetone = 19: 1) and 4-cyclohexylthiophenol.
35 Smeltepunkt: 87-89°C.Melting point: 87-89 ° C.
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Udbytte: 75,4% af det teoretiske.Yield: 75.4% of theory.
Eksempel 25 6-[4-(3,4-Dichlor-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 25 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 1 ud fra 6- (4-chlorbutoxy) -4,4-di-n-hexyl-4H-3, l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 63-64°C.Melting point: 63-64 ° C.
Udbytte: 67,9% af det teoretiske.Yield: 67.9% of theory.
10 Eksempel 26 6-[4-(4-Acetamido-phenylmercapto)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 26 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on 15 og 4-acetamido-thiophenol. Olie, RF-værdi: 0,5 (kisel-gelplade: chlorform/ethanol = 9:1) .Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one 15 and 4-acetamido-thiophenol. Oil, RF value: 0.5 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 98,2% af det teoretiske.Yield: 98.2% of theory.
Eksempel 27 6- [ 4- (3,4-Dichlor-phenylmercapto) -butoxy] -4,4-dicyclo-20 hexyl-4H-3,l-benzoxazin-2-on.Example 27 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dicyclohexyl-4H-3,l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 181-182°C.Melting point: 181-182 ° C.
25 Udbytte: 77% af det teoretiske.Yield: 77% of theory.
Eksempel 28 6- [4-(3,4-Dichlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 28 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 30 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 155-156°C.Melting point: 155-156 ° C.
Udbytte: 72,8% af det teoretiske.Yield: 72.8% of theory.
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Eksempel 29 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 29 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3 ,l-benzoxazin-2-on og 4-acetamido-thiophenol.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.
Smeltepunkt: 158°C.Melting point: 158 ° C.
Udbytte: 56,3% af det teoretiske.Yield: 56.3% of theory.
Eksempel 30 10 6-[4-(2-Pyridylmercapto)-butoxy] -4,4-dimethyl-4H-3,1-benzoxaz in-2-on.Example 30 6- [4- (2-Pyridylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 2-mercapto-pyridin.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 2-mercaptopyridine.
15 Smeltepunkt: 137-138°C.Melting point: 137-138 ° C.
Udbytte: 72,5% af det teoretiske.Yield: 72.5% of theory.
Eksempel 31 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 31 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6- (4-chlorbutoxy) -4,4-dimethyl-4H-3, l-benzoxazin-2-on og 4-cyclohexyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.
Smeltepunkt: 109-110°C.Melting point: 109-110 ° C.
Udbytte: 47% af det teoretiske.Yield: 47% of theory.
25 Eksempel 32 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 32 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6- (4-chlorbutoxy) -4,4-dimethyl-4H-3, l-benzoxazin-2-on 30 og 4-methyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4-methylthiophenol.
Smeltepunkt: 120-121°C.Melting point: 120-121 ° C.
Udbytte: 69,1% af det teoretiske.Yield: 69.1% of theory.
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Eksempel 33 6-[4-(4-Brom-3-methyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 33 6- [4- (4-Bromo-3-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4/4-dimethyl-4H-3,l-benzoxazin-2-on og 4“brom-3-methyl-thiophenol.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4 / 4-dimethyl-4H-3,1-benzoxazin-2-one and 4 ”bromo-3-methyl-thiophenol.
Smeltepunkt: 129-130°C.Melting point: 129-130 ° C.
Udbytte: 57,0% af det teoretiske.Yield: 57.0% of theory.
Eksempel 34 10 6- [4- (4-Fluor-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 34 6- [4- (4-Fluoro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-fluor-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-fluoro-thiophenol.
15 Smeltepunkt: 125-126°C.Melting point: 125-126 ° C.
Udbytte: 75,5% af det teoretiske.Yield: 75.5% of theory.
Eksempel 35 6-[4-(4-tert.Butyl-phenylmercapto)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 35 6- [4- (4-tert-Butyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-tert.butyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-tert-butyl-thiophenol.
Smeltepunkt: 119-120°C.Melting point: 119-120 ° C.
Udbytte: 76,6% af det teoretiske.Yield: 76.6% of theory.
25 Eksempel 36 6-(4-Benzylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 36 6- (4-Benzylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og benzylmercaptan.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and benzylmercaptan.
Smeltepunkt: 9 0-9 2°C.Melting point: 90-9 ° C.
Udbytte: 64,6% af det teoretiske.Yield: 64.6% of theory.
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Eksempel 37 6-(4-Methylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 37 6- (4-Methylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6- (4-chlorbutoxy) -4,4-dimethyl-4H-3, l-benzoxazin-2-on og methylmercaptan.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and methyl mercaptan.
Smeltepunkt: 98-99°C .Melting point: 98-99 ° C.
Udbytte: 75,4% af det teoretiske.Yield: 75.4% of theory.
Eksempel 38 10 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,l-benzoxazin-2-on.Example 38 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6- (4-chlorbutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-on og 4-methyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and 4-methylthiophenol.
15 Smeltepunkt: 149-150°C.Melting point: 149-150 ° C.
Udbytte: 81,4% af det teoretiske.Yield: 81.4% of theory.
Eksempel 39 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4H-3,l-benz-oxazin-2-on.Example 39 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4H-3,l-benzoxazin-2-on og 4-methyl-thiophenol .Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4H-3,1-benzoxazin-2-one and 4-methyl-thiophenol.
Smeltepunkt: 125-126°C.Melting point: 125-126 ° C.
Udbytte: 74,7% af det teoretiske.Yield: 74.7% of theory.
25 Eksempel 40 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on.Example 40 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6- (4-chlorbutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-30 2-on og 4-cyclohexyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.
Smeltepunkt: 173-175°C.Melting point: 173-175 ° C.
Udbytte: 82,3% af det teoretiske.Yield: 82.3% of theory.
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Eksempel 41 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-on.Example 41 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4H-3,l-benzoxazin-2-on og 4-cyclo-hexyl-thiophenol.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.
Smeltepunkt: 134-135°C.Melting point: 134-135 ° C.
Udbytte: 60,3% af det teoretiske.Yield: 60.3% of theory.
Eksempel 42 10 6- [4-(4-Acetamido-phenylmercapto)-butoxy]-4,4-dicyclo- hexyl-4H-3,l-benzoxazin-2-on.Example 42 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dicyclohexyl-4H-3,1-benzoxazin- 2-on og 4-acetamido-thiophenol. o 15 Smeltepunkt: 115 C (sønderdeling).Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol. o 15 Melting point: 115 C (dec.).
Udbytte: 96,8% af det teoretiske.Yield: 96.8% of theory.
Eksempel 43 6-[4-(4-Acetamido-phenylmercapto)-butoxy]-4H-3,1-benz-oxazin-2-on.Example 43 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4H-3,1-benz-oxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4H-3,l-benzoxazin-2-on og 4-acetamido-thiophenol .Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.
Smeltepunkt: 163-164°C.Melting point: 163-164 ° C.
Udbytte: 71,6% af det teoretiske.Yield: 71.6% of theory.
25 Eksempel 44 6-[2-(3,4-Dichlor-phenylmercapto)-ethoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 44 6- [2- (3,4-Dichloro-phenylmercapto) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(2-chlor-ethoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 6- (2-chloroethoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 3,4-dichloro-thiophenol.
Smeltepunkt: 145-146°C.Melting point: 145-146 ° C.
Udbytte: 69,1% af det teoretiske.Yield: 69.1% of theory.
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Eksempel 45 6-[3-(3,4-Dichlor-phenylmercapto)-propoxyj-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 45 6- [3- (3,4-Dichloro-phenylmercapto) -propoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(3-chlorpropoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 5 6- (3-chloropropoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 115-116°C.Melting point: 115-116 ° C.
Udbytte: 88,9% af det teoretiske.Yield: 88.9% of theory.
Eksempel 46 10 6-[3-(4-Cyclohexyl-phenylmercapto)-propoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 46 6- [3- (4-Cyclohexyl-phenylmercapto) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(3-chlorpropoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-cyclohexyl-thiophenol.Prepared analogously to Example 1 from 6- (3-chloropropoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.
15 Smeltepunkt: 113-114°C.Melting point: 113-114 ° C.
Udbytte: 58,1% af det teoretiske.Yield: 58.1% of theory.
Eksempel 47 6-[4-(3,4-Dimethyl-phenylmercapto)-butoxy]-4H-3,1-benz-oxazin-2-on.Example 47 6- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4H-3,1-benz-oxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4H-3,l-benzoxazin-2-on og 3,4-di-methyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4H-3,1-benzoxazin-2-one and 3,4-dimethyl-thiophenol.
Smeltepunkt: 124-125°C.Melting point: 124-125 ° C.
Udbytte: 73% af det teoretiske.Yield: 73% of theory.
25 Eksempel 48 6-[5-(4-Cyclohexyl-phenylmercapto)-pentoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 48 6- [5- (4-Cyclohexyl-phenylmercapto) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(5-brompentoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 4-cyclohexyl-thiophenol.Prepared analogously to Example 1 from 6- (5-bromopentoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4-cyclohexylthiophenol.
Smeltepunkt: 108-110°C.Melting point: 108-110 ° C.
Udbytte: 62,6% af det teoretiske.Yield: 62.6% of theory.
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Eksempel 49 6-[5-(3,4-Dichlor-phenylmercapto)-pentoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 49 6- [5- (3,4-Dichloro-phenylmercapto) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(5-brompentoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 5 6- (5-bromopentoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 110-112°C.Melting point: 110-112 ° C.
Udbytte: 81,3% af det teoretiske.Yield: 81.3% of theory.
Eksempel 50 10 6-[4-(4-tert.Butyl-phenylsulfinyl)-butoxy]-4,4-dimethyl- ' 4H-3,l-benzoxazin-2-on.Example 50 6- [4- (4-tert-Butyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-tert.butyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-tert-butyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 115°C.Melting point: 115 ° C.
Udbytte: 53,8% af det teoretiske.Yield: 53.8% of theory.
Eksempel 51 6-[4-(4-Acetamido-pheny1sulfiny1)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 51 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 180°C.Melting point: 180 ° C.
Udbytte: 55,9% af det teoretiske.Yield: 55.9% of theory.
25 Eksempel 52 6-(4-Phenylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 52 6- (4-Phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-(4-phenylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-30 oxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- (4-phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and hydrogen peroxide.
Smeltepunkt: 64-66°C.Melting point: 64-66 ° C.
Udbytte: 68,4% af det teoretiske.Yield: 68.4% of theory.
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Eksempel 53 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,1-benzoxaz in-2-on.Example 53 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-[4-(3,4-dichlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 139-140°C.Melting point: 139-140 ° C.
Udbytte: 83,8% af det teoretiske.Yield: 83.8% of theory.
Eksempel 54 10 6-[4-(4-Chlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on.Example 54 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6- [4-(4-chlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 135-136°C.Melting point: 135-136 ° C.
Udbytte: 66,3% af det teoretiske.Yield: 66.3% of theory.
Eksempel 55 6- [4- (4-Cyclohexyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on.Example 55 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4- (4-cyclohexyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 147-148°C.Melting point: 147-148 ° C.
Udbytte: 74,3% af det teoretiske.Yield: 74.3% of theory.
25 Eksempel 56 6-[4-(4-Methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on.Example 56 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-dimethyl-30 4H-3,l-benzoxazin~2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 124-125°C.Melting point: 124-125 ° C.
Udbytte: 76,0% af det teoretiske.Yield: 76.0% of theory.
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Eksempel 57 6-[4-(4-Fluoir-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on.Example 57 6- [4- (4-Fluoro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-[4-(4-fluor-phenylmercapto)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 6- [4- (4-fluoro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 118-120°C.Melting point: 118-120 ° C.
Udbytte: 79,2% af det teoretiske.Yield: 79.2% of theory.
Eksempel 58 10 6-[4-(3,4-Dimethoxy-phenylsulfinyl)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 58 6- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dimethoxy-phenylmercapto)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 157-158°C.Melting point: 157-158 ° C.
Udbytte: 82,6% af det teoretiske.Yield: 82.6% of theory.
Eksempel 59 6-[4-(4-Methoxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 59 6- [4- (4-Methoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-méthoxy-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 130-133°C.Melting point: 130-133 ° C.
Udbytte: 82,9% af det teoretiske.Yield: 82.9% of theory.
25 Eksempel 60 6-[4-(4-Hydroxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 60 6- [4- (4-Hydroxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-hydroxy-phenylmercapto)-butoxy]-4,4-dimethyl-30 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-hydroxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 157-160°C.Melting point: 157-160 ° C.
Udbytte: 44,9% af det teoretiske.Yield: 44.9% of theory.
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Eksempel 61 6-[4-(4-Biphenylylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on.Example 61 6- [4- (4-Biphenylylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-[4-(4-biphenylylmercapto)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 6- [4- (4-biphenylyl mercapto) butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 155-157°C.Melting point: 155-157 ° C.
Udbytte: 68,0% af det teoretiske.Yield: 68.0% of theory.
Eksempel 62 10 6-[4-(3-Methoxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 62 6- [4- (3-Methoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(3-methoxy-phenylmercapto)-butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3-methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Olie, RF-værdi: 0,55 (kiselgelplade; chloroform/ethanol = 9:1) .Oil, RF value: 0.55 (silica gel plate; chloroform / ethanol = 9: 1).
Udbytte: 88,4% af det teoretiske.Yield: 88.4% of theory.
C21H25N05S (403,5)C21H25N05S (403.5)
Beregnet: C 62,51 H 6,24 N 3,47 S 7,95 20 Fundet : 62,31 6,17 3,33 7,84Calculated: C 62.51 H 6.24 N 3.47 S 7.95 Found: 62.31 6.17 3.33 7.84
Eksempel 63 6-[4-(3-Methyl-phenylsulfinyl)-butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 63 6- [4- (3-Methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 25 6- [4-(3-methyl-phenylmercapto)-butoxy]-4,4-dimethyl- 4H-3,l-benzoxazin-2-on og hydrogenperoxid. Olie, RF-værdi: 0,3 (kiselgelplade? chloroform/adetone = 9:1).Prepared analogously to Example 2 from 6- [4- (3-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Oil, RF value: 0.3 (silica gel plate? Chloroform / adetone = 9: 1).
Udbytte: 87,1% af det teoretiske.Yield: 87.1% of theory.
C21H25N04S (387,5) 30 Beregnet: C 65,09 H 6,50 N 3,61 S 8,27C 21 H 25 NO 4 S (387.5) Calculated: C 65.09 H 6.50 N 3.61 S 8.27
Fundet : 64,98 6,65 3,53 8,30Found: 64.98 6.65 3.53 8.30
Eksempel 64 6-[4-(4-Amino-3,5-dibrom-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 64 6- [4- (4-Amino-3,5-dibromo-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
35 Fremstillet analogt med eksempel 2 ud fra35 Prepared analogously to Example 2 from
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70 6-{4-(4-amino-3,5-dibromphenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2—on og hydrogenperoxid. Smeltepunkt: 169-172°C.6- {4- (4-Amino-3,5-dibromophenylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 169-172 ° C.
Udbytte: 35,2% af det teoretiske.Yield: 35.2% of theory.
5 Eksempel 65 6-[4-(3,5-Di-tert.butyl-4-hydroxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 65 6- [4- (3,5-Di-tert-butyl-4-hydroxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,5-di-tert.butyl-4-hydroxy-phenylmercapto)-10 butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,5-di-tert-butyl-4-hydroxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2 on and hydrogen peroxide.
Smeltepunkt: 177-179°C.Melting point: 177-179 ° C.
Udbytte: 74,6% af det teoretiske.Yield: 74.6% of theory.
Eksempel 66 15 6-[4-(4-Brom-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on.Example 66 6- [4- (4-Bromo-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-brom-phenylmercapto)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-bromo-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.
20 Smeltepunkt: 137-138°C.Melting point: 137-138 ° C.
Udbytte: 79,8% af det teoretiske.Yield: 79.8% of theory.
Eksempel 67 6-[4-(4-Methyl-phenylsulfinyl)-butoxy]-4H-3,1-benzoxa-zin-2-on.Example 67 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-methyl-phenylmercapto)-butoxy]-4H-3,1-benzoxa-zin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 143-144°C.Melting point: 143-144 ° C.
Udbytte: 82,2% af det teoretiske.Yield: 82.2% of theory.
30 Eksempel 68 6-[4-(4-Cyclohexyl-phenylsulfinyl)-butoxy]-4H-3,1-benzoxazin-2-on.Example 68 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4- (4-cyclohexyl-phenylmercapto)-butoxy]-4H-3,1- 71Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4H-3,1- 71
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benzoxazin-2-on og hydrogenperoxid.benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 118-119°C.Melting point: 118-119 ° C.
Udbytte: 81,5% af det teoretiske.Yield: 81.5% of theory.
Eksempel 69 5 6—[4—(4-Acetamido-phenylsulfinyl)-butoxy]-4H-3,1- benzoxazin-2-on.Example 69 5- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-acetamido-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
10 Smeltepunkt: 183-184°C.Melting point: 183-184 ° C.
Udbytte: 84,0% af det teoretiske.Yield: 84.0% of theory.
Eksempel 70 6-[4-(3,4-Dimethyl-phenylsulfinyl)-butoxy]-4H-3,1-benzoxazin-2-on.Example 70 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
15 Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dimethyl-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt; 119-120°C.Melting point; 119-120 ° C.
Udbytte: 57,0% af det teoretiske.Yield: 57.0% of theory.
20 Eksempel 71 6-(4-Phenylsulfinyl-butoxy)-4H-3,l-benzoxazin-2-on.Example 71 6- (4-Phenylsulfinyl-butoxy) -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-(4-phenylmercapto-butoxy)-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- (4-phenylmercapto-butoxy) -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
25 Smeltepunkt: 115-116°C.Melting point: 115-116 ° C.
Udbytte: 66,7% af det teoretiske.Yield: 66.7% of theory.
Eksempel 72 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4H-3,1-benzoxazin-2-on.Example 72 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
30 Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dichlor-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 169-170°C.Melting point: 169-170 ° C.
Udbytte: 91,8% af det teoretiske.Yield: 91.8% of theory.
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Eksempel 73 6- [4-(4-Chlor-phenylsulfinyl)-butoxy]-4H-3,1-benzoxazin-2-on.Example 73 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-[4-(4-chlor-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 6- [4- (4-chloro-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 169-171°C.Melting point: 169-171 ° C.
Udbytte: 86,0% af det teoretiske.Yield: 86.0% of theory.
Eksempel 74 10 6-(4-Benzylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benzoxa-zin-2-on.Example 74 6- (4-Benzylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-(4-benzylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- (4-benzylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 122°C.Melting point: 122 ° C.
Udbytte: 71,0% af det teoretiske.Yield: 71.0% of theory.
Eksempel 75 6-(4-Methylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 75 6- (4-Methylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6- (4-methylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- (4-methylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 124-126°C.Melting point: 124-126 ° C.
Udbytte: 68,1% af det teoretiske.Yield: 68.1% of theory.
25 Eksempel 76 6- (4-Cyclohexylsulf inyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxaz in-2-on.Example 76 6- (4-Cyclohexylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6- (4-cyclohexylmercapto-butoxy) -4,4-dimethyl-4H-3, Ι-ΙΟ benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- (4-cyclohexylmercapto-butoxy) -4,4-dimethyl-4H-3, Ι-ΙΟ benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 115°C.Melting point: 115 ° C.
Udbytte: 76,9% af det teoretiske.Yield: 76.9% of theory.
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Eksempel 77 6-[4-(4-Acetamido-phenylsulfinyl)-butoxy]-4 ,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on.Example 77 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-[4-(4-acetamido-phenylmercapto)-butoxy]-4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 206-207°C.Melting point: 206-207 ° C.
Udbytte: 53,5% af det teoretiske.Yield: 53.5% of theory.
Eksempel 78 10 6-[4-(4-Methyl-phenylsulfinyl)-butoxy]-4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on.Example 78 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 200-201°C.Melting point: 200-201 ° C.
Udbytte: 62,0% af det teoretiske.Yield: 62.0% of theory.
Eksempel 79 6-[4-(4-Cyclohexyl-phenylsulfinyl)-butoxy]-4,4-di-cyclohexyl-4H-3,l-benzoxazin-2-on.Example 79 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-di-cyclohexyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-cyclohexyl-phenylmercapto)-butoxy]-4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: fra 146°C (sønderdeling).Melting point: from 146 ° C (dec.).
Udbytte: 89,3% af det teoretiske.Yield: 89.3% of theory.
25 Eksempel 80 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on.Example 80 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dichlor-phenylmercapto)-butoxy]-4,4-dicyclo-30 hexyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 186-187°C.Melting point: 186-187 ° C.
Udbytte: 49,2% af det teoretiske.Yield: 49.2% of theory.
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Eksempel 81 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 81 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3, l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 78-79°C.Melting point: 78-79 ° C.
Udbytte: 87,3% af det teoretiske.Yield: 87.3% of theory.
Eksempel 82 10 6- [4- (4-Cyclohexyl-phenylsulfinyl)-butoxy] -4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 82 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 72-75°C.Melting point: 72-75 ° C.
Udbytte: 71,4% af det teoretiske.Yield: 71.4% of theory.
. Eksempel 83 6- [4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.. Example 83 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6- [4- (3,4-dichlor-phenylmercapto)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 8 3-8 5°C.Melting point: 8 3-8 5 ° C.
Udbytte: 71,7% af det teoretiske.Yield: 71.7% of theory.
25 Eksempel 84 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 84 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-di-n-30 hexyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Olie, RF-værdi: 0,48 (kiselgelplade: chloroform/ethanol= 9:1) .Oil, RF value: 0.48 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 43,8% af det teoretiske.Yield: 43.8% of theory.
C32H46N2°5S (570,79) 35 Beregnet: C 67,34 H 8,12 N 4,91 S 5,62 75C32H46N2 ° 5S (570.79) Calculated: C 67.34 H 8.12 N 4.91 S 5.62 75
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Fundet: C 67,52 H 7,94 N 4,95 S 5,78Found: C 67.52 H 7.94 N 4.95 S 5.78
Eksempel 85 6- [2- (3,4-Dichlor-phenylsulfinyl)-ethoxy]-4,4-dimethy1-4H-3,l-benzoxazin-2-on.Example 85 6- [2- (3,4-Dichloro-phenylsulfinyl) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 2 ud fra 6- [2-(3,4-dichlor-phenylmercapto)-ethoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [2- (3,4-dichloro-phenylmercapto) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 200-201°C.Melting point: 200-201 ° C.
Udbytte: 63,3% af det teoretiske.Yield: 63.3% of theory.
10 Eksempel 86 6— [ 3—(3,4-Dichlor-phenylsulfinyl)-propoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 86 6 - [3- (3,4-Dichloro-phenylsulfinyl) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6- [3-(3,4-dichlor-phenylmercapto)-propoxy]-4,4-dimethyl-15 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [3- (3,4-dichloro-phenylmercapto) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 157-158°C.Melting point: 157-158 ° C.
Udbytte: 76,3% af det teoretiske.Yield: 76.3% of theory.
Eksempel 87 6- [3- (4-Cyclohexyl-phenylsulfinyl)-propoxy]-4,4-dimethyl-20 4H-3,l-benzoxazin-2-on.Example 87 6- [3- (4-Cyclohexylphenylsulfinyl) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6- [3- (4-cyclohexyl-phenylmercapto)-propoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [3- (4-cyclohexyl-phenylmercapto) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Olie, RF-værdi: 0,45 (kiselgelplade: chloroform/ethanol = 25 9:1).Oil, RF value: 0.45 (silica gel plate: chloroform / ethanol = 25: 9).
Udbytte: 96,3% af det teoretiske.Yield: 96.3% of theory.
C25H31N04S (441,59)C25H31NO4S (441.59)
Beregnet: C 68,00 H 7,08 N 3,17 S 7,26Calculated: C 68.00 H 7.08 N 3.17 S 7.26
Fundet : 67,75 7,01 3,17 7,13 30 Eksempel 88 6- [ 5- (4-Cyclohexyl-phenylsulfinyl)pentoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Found: 67.75 7.01 3.17 7.13 Example 88 6- [5- (4-Cyclohexyl-phenylsulfinyl) pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6- [5- (4-cyclohexyl-phenylmercapto)-pentoxy]-4,4-di- 76Prepared analogously to Example 2 from 6- [5- (4-cyclohexyl-phenylmercapto) -pentoxy] -4,4-di-76
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methyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.methyl 4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Olie, RF-værdi: 0,45 (kiselgelplade: chloroform/etha-nol = 9:1).Oil, RF value: 0.45 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 63,9% af det teoretiske.Yield: 63.9% of theory.
5 C27H35N04S (469,65)C27H35NO4S (469.65)
Beregnet: C 69,05 H 7,51 N 2,98 S 6,83Calculated: C 69.05 H 7.51 N 2.98 S 6.83
Fundet : 70,26 7,74 2,91 6,87Found: 70.26 7.74 2.91 6.87
Eksempel 89 6-[5-(3,4-Dichlor-phenylsulfinyl)-pentoxy]-4,4-dime-10 thyl-4H-3,l-benzoxazin-2-on.Example 89 6- [5- (3,4-Dichloro-phenylsulfinyl) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[5-(3,4-dichlor-phenylmercapto)-pentoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [5- (3,4-dichloro-phenylmercapto) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 119-120°C.Melting point: 119-120 ° C.
15 Udbytte: 83,8% af det teoretiske.Yield: 83.8% of theory.
Eksempel 90 6-[4-(3,4-Dimethoxy-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,1-benzoxaz in-2-on.Example 90 6- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 20 6-[4-(3,4-dimethoxy-phenylsulfinyl)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.
Smeltepunkt: 162-163°C.Melting point: 162-163 ° C.
Udbytte: 51,3% af det teoretiske.Yield: 51.3% of theory.
25 Eksempel 91 6-[4-(4-Methoxy-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,1-benzoxaz in-2-on.Example 91 6- [4- (4-Methoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-methoxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-30 4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-methoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate-hydroxamic acid ethyl ester.
Smeltepunkt: 134-140°C.Melting point: 134-140 ° C.
Udbytte: 47,8% af det teoretiske.Yield: 47.8% of theory.
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Eksempel 92 6-[4-(4-Hydroxy-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 92 6- [4- (4-Hydroxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 5 6-[4-(4-hydroxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 5- [4- (4-hydroxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester.
Smeltepunkt: 182-184°C.Melting point: 182-184 ° C.
Udbytte: 28,4% af det teoretiske.Yield: 28.4% of theory.
10 Eksempel 93 6-[4-(3-Methoxy-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 93 6- [4- (3-Methoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3-methoxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-15 4H-3,l-benzoxazin-2-on og O-mesitylensylfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3-methoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylensylphonyl-acetyl-hydroxamic acid ethyl ester.
Smeltepunkt: 102-105°C.Melting point: 102-105 ° C.
Udbytte: 31,9% af det teoretiske.Yield: 31.9% of theory.
Eksempel 94 20 6-[4-(4-Biphenylylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 94 6- [4- (4-Biphenylylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-biphenylylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-25 syre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-biphenylylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 184-186°C.Melting point: 184-186 ° C.
Udbytte: 68,5% af det teoretiske.Yield: 68.5% of theory.
Eksempel 95 6-[4-(4-Amino-3,5-dibrom-phenylsulfoximino)-butoxy]-30 4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 95 6- [4- (4-Amino-3,5-dibromo-phenylsulfoxymino) -butoxy] -30,4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-amino-3,5-dibrom-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfinyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-amino-3,5-dibromo-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfinyl -acethydroxamsyre acid ethyl ester.
35 Smeltepunkt: 206-208°C.Melting point: 206-208 ° C.
7878
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Udbytte: 73,8% af det teoretiske.Yield: 73.8% of theory.
Eksempel 96 6-[4-(3,5-Di-tert.butyl-4-hydroxy-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 96 6- [4- (3,5-Di-tert-butyl-4-hydroxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,5-di-tert.butyl-4-hydroxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 0-mesi-tylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,5-di-tert-butyl-4-hydroxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2- one and 0-mesethylenesulfonylacetydroxamic acid ethyl ester.
Smeltepunkt: 176-178°C.Melting point: 176-178 ° C.
10 Udbytte: 65,8% af det teoretiske.Yield: 65.8% of theory.
Eksempel 97 6- [4- (3-Methyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 97 6- [4- (3-Methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 15 6-[4-(3-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl- 4H-3 ,l-benzoxazin-2-on og O-mesitylensulfonyl-acethy-droxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethyroxamic acid. ethyl ester.
Smeltepunkt: 118-120°C.Melting point: 118-120 ° C.
Udbytte: 33% af det teoretiske.Yield: 33% of theory.
20 Eksempel 98 6-[4-(4-Fluor-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 98 6- [4- (4-Fluoro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4—fluor-phenylsulfinyl)-butoxy]-4,4-dimethyl-25 4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet- hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-fluoro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester.
Smeltepunkt: 136-138°C.Melting point: 136-138 ° C.
Udbytte: 30,8% af det teoretiske.Yield: 30.8% of theory.
Eksempel 99 30 6- [4- (4-Brom-phenylsulfoximino) -butoxy] -4,4-dimethyl- 4H-3,l-benzoxazin-2-on.Example 99 6- [4- (4-Bromo-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6- [4- (4-brom-phenylsulf inyl) -butoxy] -4,4-dimethyl-4H- 3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam- 79Prepared analogously to Example 6 from 6- [4- (4-bromo-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxam-79
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syre-ethylester.acid ethyl ester.
Smeltepunkt: 155-157°C.Melting point: 155-157 ° C.
Udbytte: 50% af det teoretiske.Yield: 50% of theory.
Eksempel 100 5 6-[4-(4- Brom-3-methyl-phenylsulfoximino) -butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 100 6- [4- (4- Bromo-3-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-brom-3-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-10 acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-bromo-3-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-10 acethydroxamsyre acid ethyl ester.
Smeltepunkt: 153-154°C.Melting point: 153-154 ° C.
Udbytte: 63,6% af det teoretiske.Yield: 63.6% of theory.
Eksempel 101 6-[4-(4-Cyclohexyl-phenylsulfoximino)-butoxy]-4,4-15 dimethyl-4H-3,l-benzoxazin-2-on.Example 101 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester .
20 Smeltepunkt: 168-169°C.Melting point: 168-169 ° C.
Udbytte: 52,8% af det teoretiske.Yield: 52.8% of theory.
Eksempel 102 6-[4-(4-Methyl-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 102 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-hydroxamic acid. ethyl ester.
Smeltepunkt: 147-148°C.Melting point: 147-148 ° C.
30 Udbytte: 59,2% af det teoretiske.Yield: 59.2% of theory.
Eksempel 103 6-(4-Phenylsulfoximino-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on.Example 103 6- (4-Phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 80Prepared analogously to Example 6 from 80
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6-(4-phenylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.6- (4-Phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 152°C.Melting point: 152 ° C.
5 Udbytte: 71,7% af det teoretiske.Yield: 71.7% of theory.
Eksempel 104 6-[4-(4-Chlor-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 104 6- [4- (4-Chloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud. fra 10 6- [4-(4-chlor-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H- 3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-syre-ethylester.Prepared analogously to Example 6 out. from 6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester.
Smeltepunkt: 132°C.Melting point: 132 ° C.
Udbytte:61,6% af det teoretiske.Yield: 61.6% of theory.
15 Eksempel 105 6-[4-(4-tert.Butyl-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 105 6- [4- (4-tert-Butyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-tert.butyl-phenylsulfinyl)-butoxy]-4,4-dime-20 thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-tert-butyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.
Smeltepunkt: 187°C.Melting point: 187 ° C.
Udbytte: 72% af det teoretiske.Yield: 72% of theory.
Eksempel 106 25 6-[4-(4-Acetamido-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 106 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6- [4- (4-acetamido-phenylsulf inyl) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-3 0 hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-30 hydroxamic acid ethyl ester.
Smeltepunkt: 185°C.Melting point: 185 ° C.
Udbytte: 44% af det teoretiske.Yield: 44% of theory.
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Eksempel 107 6-[4-(4-Methyl-phenylsulfoximino)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 107 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 5 6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-di-n-hexyl-4H-3/l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 5- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3/1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.
Smeltepunkt: 89-91°C.Melting point: 89-91 ° C.
Udbytte: 87,5% af det teoretiske.Yield: 87.5% of theory.
10 Eksempel 108 6-[4-(4-Cyclohexyl-phenylsulfoximino)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 108 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-cyclohexyl-phenylsulfinyl)-butoxy]-4,4-di-n-15 hexyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.
Smeltepunkt: 78-80°C.Melting point: 78-80 ° C.
Udbytte: 48,3% af det teoretiske.Yield: 48.3% of theory.
Eksempel 109 20 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 109 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dichlor-phenylsulfonyl)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-25 acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfonyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl -25 acetyl hydroxamic acid ethyl ester.
Smeltepunkt: 106-108°C.Melting point: 106-108 ° C.
Udbytte: 66,9% af det teoretiske.Yield: 66.9% of theory.
Eksempel 110 6-[4-(4-Acetamido-phenylsulfoximino)-butoxy]-4,4-di-n-30 hexyl-4H-3,l-benzoxazin-2-on.Example 110 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-acetamido-phenylsulfinyl)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and O-mesitylenesulfonyl-acetydroxamic acid ethyl ester.
35 Smeltepunkt: 146-148°C.Melting point: 146-148 ° C.
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Udbytte: 78% af det teoretiske.Yield: 78% of theory.
Eksempel 111 6-[4-(4-Acetamido-phenylsulfoximino)-butoxy]-4,4-di-cyclohexyl-4H-3,l-benzoxazin-2-on.Example 111 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-di-cyclohexyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-acetamido-phenylsulfinyl)-butoxy]-4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid. ethyl ester.
Smeltepunkt: 149-150°C.Melting point: 149-150 ° C.
10 Udbytte: 54% af det teoretiske.Yield: 54% of theory.
Eksempel 112 6- [4-(4-Methyl-phenylsulfoximino) -butoxy] -4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on.Example 112 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 15 6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid. ethyl ester.
Smeltepunkt: 176-177°C.Melting point: 176-177 ° C.
Udbytte; 58,6% af det teoretiske.Yield; 58.6% of theory.
20 Eksempel 113 6-[4-(4-Cyclohexyl-phenylsulfoximino)-butoxy]-4,4-di-cyclohexyl-4H-3,l-benzoxazin-2-on.Example 113 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-di-cyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-cyclohexyl-phenylsulfinyl)-butoxy]-4,4-dicyclo-25 hexyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acetr hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetre hydroxamic acid ethyl ester.
Smeltepunkt: 219-220°C.Melting point: 219-220 ° C.
Udbytte: 73,2% af det teoretiske.Yield: 73.2% of theory.
Eksempel 114 30 6-[4-(4-Methyl-phenylsulfoximino)-butoxy]-4H-3,1-benz-oxazin-2-on.Example 114 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4H-3,1-benz-oxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4H-3,1-benzoxazxn-2-on og O-mesitylensulfonyl-acethydraxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetydraxamic acid ethyl ester.
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Smeltepunkt: 153-154°C.Melting point: 153-154 ° C.
Udbytte: 60% af det teoretiske.Yield: 60% of theory.
Eksempel 115 6-[4-(4-Cyclohexyl-phenylsulfoximino)-butoxy]-4H-3,1-5 benzoxazin-2-on.Example 115 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4H-3,1-5-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-cyclohexyl-phenylsulfinyl)-butoxy]-4H-3,1-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-syre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one and O-mesitylene-sulfonyl-acethydroxamic acid ethyl ester.
10 Smeltepunkt: 187-188°C.Melting point: 187-188 ° C.
Udbytte: 65% af det teoretiske.Yield: 65% of theory.
Eksempel 116 6-[4-(4-Acetamido-phenylsulfoximino)-butoxy]-4H-3,1-benzoxazin-2-on.Example 116 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.
15 Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-acetamido-phenylsulfinyl)-butoxy]-4H-3,1-benz-oxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester .Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4H-3,1-benz-oxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester.
Smeltepunkt: 135-137°C.Melting point: 135-137 ° C.
20 Udbytte: 64,7% af det teoretiske.Yield: 64.7% of theory.
Eksempel 117 6-[5-(3,4-Dichlor-phenylsulfoximino)-pentoxy]-4,4-di- methyl-4H-3,l-benzoxazin-2-on.Example 117 6- [5- (3,4-Dichloro-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 25 6-[5-(3,4-dichlor-phenylsulfinyl)-pentoxy]-4,4-dime- thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet- hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [5- (3,4-dichloro-phenylsulfinyl) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamic acid ethyl ester.
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Smeltepunkt: 169-170 C.Melting point: 169-170 ° C
Udbytte: 85,7% af det teoretiske.Yield: 85.7% of theory.
30 Eksempel 118 6-[5-(4-Cyclohexyl-phenylsulfoximino)-pentoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 118 6- [5- (4-Cyclohexyl-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[5-(4-cyclohexyl-phenylsulfinyl)-pentoxy]-4,4-dime- 84Prepared analogously to Example 6 from 6- [5- (4-cyclohexyl-phenylsulfinyl) -pentoxy] -4,4-dimethyl-84
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thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.thyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acetate hydroxamic acid ethyl ester.
Smeltepunkt: 110-111°C.Melting point: 110-111 ° C.
Udbytte: 67,1% af det teoretiske.Yield: 67.1% of theory.
5 Eksempel 119 6- [3-(3,4-Dichlor-phenylsulfoximino)-propoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 119 6- [3- (3,4-Dichloro-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6- [3-(3,4-dichlor-phenylsulfinyl)-propoxy]-4,4-dime-10 thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [3- (3,4-dichloro-phenylsulfinyl) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.
Smeltepunkt: 135-136°C.Melting point: 135-136 ° C.
Udbytte: 67,8% af det teoretiske.Yield: 67.8% of theory.
Eksempel 120 15 6- [3-(4-Cyclohexyl-phenylsulfoximino)-propoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 120 6- [3- (4-Cyclohexyl-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6- [3-(4-cyclohexyl-phenylsulfinyl)-propoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-2 0 hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [3- (4-cyclohexyl-phenylsulfinyl) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-2 0 hydroxamic acid ethyl ester.
Smeltepunkt: 175-176°C.Melting point: 175-176 ° C.
Udbytte: 50,3% af det teoretiske.Yield: 50.3% of theory.
Eksempel 121 6-[2-(3,4-Dichlor-phenylsulfoximino)-ethoxy]-4,4-dime-25 thyl-4H-3,l-benzoxazin-2-on.Example 121 6- [2- (3,4-Dichloro-phenylsulfoxymino) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[2- (3,4-dichlor-phenylsulfinyl)-ethoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [2- (3,4-dichloro-phenylsulfinyl) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl hydroxamic acid ethyl ester.
30 Smeltepunkt: 139-140°C.Melting point: 139-140 ° C.
Udbytte: 64% af det teoretiske.Yield: 64% of theory.
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Eksempel 122 6-(4-Cyclohexylsulfoximino-butoxy)-4,4-dimethyl-4H-3,l-benzoxaz in-2-on.Example 122 6- (4-Cyclohexylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 5 6-(4-cyclohexylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1- benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 5 6- (4-cyclohexylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetydroxamic acid ethyl ester.
Smeltepunkt: 108-110°C.Melting point: 108-110 ° C.
Udbytte: 28% af det teoretiske.Yield: 28% of theory.
10 Eksempel 123 6-(4-Benzylsulfoximino-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 123 6- (4-Benzylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6- (4-benzylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz-15 oxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- (4-benzylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and O-mesitylenesulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 132-138°C.Melting point: 132-138 ° C.
Udbytte: 75% af det teoretiske.Yield: 75% of theory.
Eksempel 124 20 6-(4-n-0ctylsulfoximino-butoxy)-4,4-dimethyl-4H-3,1- benzoxazin-2-on.Example 124 6- (4-n-Octylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-(4-n-octylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-25 ethylester.Prepared analogously to Example 6 from 6- (4-n-octylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and O-mesitylenesulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 82°C.Melting point: 82 ° C.
Udbytte: 73,2% af det teoretiske.Yield: 73.2% of theory.
Eksempel 125 6-[4-(4-Chlor-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-30 2-on.Example 125 6- [4- (4-Chloro-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 5 ud fra 6-hydroxy-4H-3,l-benzoxazin-2-on og 4-(4-chlor-phenyl-mercapto)-butylchlorid (fremstillet ud fra 4-(4-chlor-phenylmercapto)-butanol og thionylchlorid.Prepared analogously to Example 5 from 6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (4-chloro-phenyl-mercapto) -butyl chloride (prepared from 4- (4-chloro-phenyl-mercapto) - butanol and thionyl chloride.
35 Olie, RF-værdi: 0,25 (kiselgel: petroleumsether/cyclo- hexan = 1:1).Oil, RF value: 0.25 (silica gel: petroleum ether / cyclohexane = 1: 1).
Smeltepunkt: 143-144°C.Melting point: 143-144 ° C.
Udbytte: 28% af det teoretiske.Yield: 28% of theory.
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Eksempel 126 5 6- [4- (3,4-Dichlor-phenylmercapto) -butoxy] -4H-3,l-benz- oxazin-2-on.Example 126 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 5 ud fra 6-hydroxy-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylmercapto)-butylbromid (fremstillet ud fra 10 3,4-dichlorthiophenol og 1,4-dibrom-butan, KpQ ^ 153-160°C).Prepared analogously to Example 5 from 6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylmercapto) -butyl bromide (prepared from 10 3,4-dichloro-thiophenol and 1.4 -dibromo-butane, Kp
Smeltepunkt: 128-129°C.Melting point: 128-129 ° C.
Udbytte: 57% af det teoretiske.Yield: 57% of theory.
Eksempel 127 15 6-(4-Phenylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz- oxazin-2-on.Example 127 6- (4-Phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 5 ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-phe-nylmercapto-butylbromid (Kp g 03 mb: 95-104°C)· 20 Smeltepunkt: 108-109°C.Prepared analogously to Example 5 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylmercapto-butyl bromide (Kp g 03 mb: 95-104 ° C) · 20 Melting point: 108-109 ° C.
Udbytte: 52,5% af det teoretiske.Yield: 52.5% of theory.
Eksempel 128 6-[4-(3,4-Dichlor-phenylmercapto)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 128 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 5 ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylmercapto)-butylbromid.Prepared analogously to Example 5 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylmercapto) -butyl bromide.
Smeltepunkt: 155-156°C.Melting point: 155-156 ° C.
Udbytte: 53% af det teoretiske.Yield: 53% of theory.
30 Eksempel 129 6-[4-(4-Chlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H- 3,l-benzoxazin-2-on.Example 129 6- [4- (4-Chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 5 ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(4-chlor-phenylmercapto)-butylchlorid.Prepared analogously to Example 5 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-chloro-phenylmercapto) -butyl chloride.
Smeltepunkt: 150-151°C.Melting point: 150-151 ° C.
Udbytte: 55,6% af det teoretiske.Yield: 55.6% of theory.
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Eksempel 130 5 6-[4-(3,4-Dimethyl-phenylsulfoximino)-butoxy]-4H-3,1- benzoxazin-2-on.Example 130 6- [4- (3,4-Dimethyl-phenylsulfoximino) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6- [4- (3,4-dimethyl-phenylsulfinyl)-butoxy]-4H-3,1-benz-oxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-10 ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4H-3,1-benz-oxazin-2-one and O-mesitylene-sulfonyl-acetyl-hydroxamic acid-ethyl ester.
Smeltepunkt: 169-170°C.Melting point: 169-170 ° C.
Udbytte: 82,5% af det teoretiske.Yield: 82.5% of theory.
Eksempel 131 6- (4-(3,4-Dimethyl-phenylsulfoximino)-butoxy]-4,4-di-15 methyl-4H-3,l-benzoxazin-2-on.Example 131 6- (4- (3,4-Dimethyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dimethyl-phenylsulfinyl)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetroxamic acid ethyl ester.
20 Smeltepunkt: 162-163°C.Melting point: 162-163 ° C.
Udbytte: 70,4% af det teoretiske.Yield: 70.4% of theory.
Eksempel 132 6-[4-(3,4-Dimethyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 132 6- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dimethyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethylthiophenol.
Smeltepunkt: 122-123°C.Melting point: 122-123 ° C.
Udbytte: 75,3% af det teoretiske.Yield: 75.3% of theory.
30 Eksempel 133 6-[6-(3,4-Dichlor-phenylmercapto)-hexyloxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 133 6- [6- (3,4-Dichloro-phenylmercapto) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(6-bromhexyloxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 6- (6-bromohexyloxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 102-103°C.Melting point: 102-103 ° C.
Udbytte: 77,4% af det teoretiske.Yield: 77.4% of theory.
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Eksempel 134 5 6-[6-(3,4-Dimethoxy-phenylmercapto)-hexyloxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 134 6- [6- (3,4-Dimethoxy-phenylmercapto) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(6-bromhexyloxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dimethoxy-thiophenol.Prepared analogously to Example 1 from 6- (6-bromohexyloxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.
10 Smeltepunkt: 153-154°C.Melting point: 153-154 ° C.
Udbytte: 89,4% af det teoretiske.Yield: 89.4% of theory.
Eksempel 135 6-(4-Phenylsulfonyl-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 135 6- (4-Phenylsulfonyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
15 Fremstillet analogt med eksempel 4 ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-phenylsulfonyl-butylbromid (smeltepunkt: 57-58°C). Smeltepunkt: 155-156°C.Prepared analogously to Example 4 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfonyl-butyl bromide (m.p. 57-58 ° C). Melting point: 155-156 ° C.
Udbytte: 53,7% af det teoretiske.Yield: 53.7% of theory.
20 Eksempel 136 6-[6-(3,4-Dichlor-phenylsulfoximino)-hexyloxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 136 6- [6- (3,4-Dichloro-phenylsulfoxymino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[6-(3,4-dichlor-phenylsulfonyl)-hexyloxy]-4,4-dime-25 thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [6- (3,4-dichloro-phenylsulfonyl) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.
Smeltepunkt: 135-136°C.Melting point: 135-136 ° C.
Udbytte: 84,5% af det teoretiske.Yield: 84.5% of theory.
Eksempel 137 30 6—[4—(3,4-Dichlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 137 6 - [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylmercapto)-butyl-bromid (Kp g ^ m^: 89Prepared analogously to Example 4 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylmercapto) -butyl bromide (Kp g : 89
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153-160°C) .153-160 ° C).
Smeltepunkt: 152-153°C.Melting point: 152-153 ° C.
Udbytte: 63,4% af det teoretiske.Yield: 63.4% of theory.
Eksempel 138 5 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4-ethyl-4H- 3,l-benzoxazin-2-on.Example 138 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4-ethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 4-ethyl-6-hydroxy-4H-3,l-benzoxazin-2-on og 4-(3,4-di-chlor-phenylsulfinyl)-butylbromid.Prepared analogously to Example 4 from 4-ethyl-6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.
10 Smeltepunkt: 83-84°C.Melting point: 83-84 ° C.
Udbytte: 61,9% af det teoretiske.Yield: 61.9% of theory.
Eksempel 139 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4-isopropyl-4H-3,1-benzoxazin-2-on, 15 Fremstillet analogt med eksempel 4 ud fra 6-hydroxy-4-isoproyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylsulfinyl)-butylbromid.Example 139 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one Prepared analogously to Example 4 from 6-hydroxy-4-one isoproyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.
Smeltepunkt: 73-75°C.Melting point: 73-75 ° C.
Udbytte: 48,2% af det teoretiske.Yield: 48.2% of theory.
20 Eksempel 140 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4-ethyl-4H-3,l-benzoxazin-2-on.Example 140 6- [4- (3,4-Dichloro-phenylsulfoximino) -butoxy] -4-ethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4-ethyl-4H-25 3>l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-syre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4-ethyl-4H-3,3-1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 132-133°C.Melting point: 132-133 ° C.
Udbytte: 60% af det teoretiske.Yield: 60% of theory.
Eksempel 141 30 6-[4-(3,4-Dichlor-N-p-toluehsulfonyl-phenylsulfoximino)- butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 141 6- [4- (3,4-Dichloro-N-p-toluehsulfonyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 12 ud fra 6-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og p-toluensulfonsyrechlo- 90Prepared analogously to Example 12 from 6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and p-toluenesulfonic acid chloro-90
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rid.chloride.
Smeltepunkt: 174-175°C.Melting point: 174-175 ° C.
Udbytte: 78,4% af det teoretiske.Yield: 78.4% of theory.
Eksempel 142 5 6-[4-(3,4-Dichlor-N-benzoyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 142 6- [4- (3,4-Dichloro-N-benzoyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 12 ud fra 6-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og benzoylchlorid.Prepared analogously to Example 12 from 6- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and benzoyl chloride.
10 Smeltepunkt: 189-190°C.Melting point: 189-190 ° C.
Udbytte: 67,6% af det teoretiske.Yield: 67.6% of theory.
Eksempel 143 6-[4-(3,4-Dimethoxy-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 143 6- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
15 Til en opløsning af 1 g (0,0022 mol) 6-[4-(3,4- dimethoxy-phenyl sulf oximino) -butoxy] -4,4-dimethyl-4H- 3,l-benzoxazin-2-on.i Γ0 ml iseddikesyre sattes 1,5 ml acetanhydrid, og der omrørtes i 3 timer ved stue temperatur. Efter tilsætning af isvand ekstraheredes 20 med chloroform, chlorof ormf asen vaskedes med vand og tørredes med natriumsuifat, hvorpå chloroformen afdestil-leredes og remanenseh omkrystalliseres i eddikesyreethyl-ester.To a solution of 1 g (0.0022 mol) of 6- [4- (3,4-dimethoxy-phenyl sulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one In ml0 ml glacial acetic acid was added 1.5 ml of acetanhydride and stirred for 3 hours at room temperature. After the addition of ice water, 20 was extracted with chloroform, the chloroform or ash was washed with water and dried over sodium sulfate, then the chloroform was distilled off and recrystallized from acetic acid ethyl ester.
Smeltepunkt: 155-157°C.Melting point: 155-157 ° C.
25 Udbytte: 0,95 g (88% af det teoretiske).Yield: 0.95 g (88% of theory).
Eksempel 144 6-[4-(4-Phenyl-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 144 6- [4- (4-Phenyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 30 6-[4-(4-phenyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-phenyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 106-108°C.Melting point: 106-108 ° C.
Udbytte: 94,7% af det teoretiske.Yield: 94.7% of theory.
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Eksempel 145 6-[4-(3,S-Di-tert-butyl^-hydroxy-N-acetyl-phenyl-sulfoximino) -butoxy] -4,4-dimethyl-4H-3, l-benzoxazin-2-on. Fremstillet analogt med eksempel 143 ud fra 5 6-[4-(3,5-di-tert.butyl-4-hydroxy-phenyIsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acet-anhydrid.Example 145 6- [4- (3, 5-Di-tert-butyl 4-hydroxy-N-acetyl-phenyl-sulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one . Prepared analogously to Example 143 from 5- [4- (3,5-di-tert-butyl-4-hydroxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2 on and acet anhydride.
Smeltepunkt: 206-207°C.Melting point: 206-207 ° C.
Udbytte: 93,1% af det teoretiske.Yield: 93.1% of theory.
10 Eksempel 146 6-[4-(4-Amino-3,5-dibrom-N-acetyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 146 6- [4- (4-Amino-3,5-dibromo-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-amino-3,5-dibrom-phenylsulfoximino)-butoxy]-15 4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid. Smeltepunkt: 198-200°C.Prepared analogously to Example 143 from 6- [4- (4-amino-3,5-dibromo-phenylsulfoxymino) -butoxy] -15 4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 198-200 ° C.
Udbytte: 86,2% af det teoretiske.Yield: 86.2% of theory.
Eksempel 147 6- [4- (4-tert .Butyl-N-acetyl-phenylsulfoximino) -butoxy] -20 4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 147 6- [4- (4-tert-Butyl-N-acetyl-phenylsulfoxymino) -butoxy] -20 4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6- [4- (4-tert. butyl-phenylsulf oximino) -butoxy] -4,4-di-methyl~4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-tert-butyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 235-237°C.Melting point: 235-237 ° C.
25 Udbytte: 92,9% af det teoretiske.Yield: 92.9% of theory.
Eksempel 148 6-[4-(4-Me thyl-N-acetyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 148 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 30 6-[4-(4-methyl-phenyIsulfoximino) -butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 109-110°C.Melting point: 109-110 ° C.
Udbytte: 83,6% af det teoretiske.Yield: 83.6% of theory.
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Eksempel 149 6-[4-(4-Brom-3-methyl-N-acetyl-phenylsulfoximino)-but-oxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 149 6- [4- (4-Bromo-3-methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[4-(4-brom-3-methyl-phenylsulfoximino)-butoxy]-4,4- dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 6- [4- (4-bromo-3-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 152-154°C.Melting point: 152-154 ° C.
Udbytte: 85,5% af det teoretiske.Yield: 85.5% of theory.
Eksempel 150 10 6-[4-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-butoxy]- 4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 150 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Smeltepunkt: 156-158°C.Melting point: 156-158 ° C.
Udbytte: 91,3% af det teoretiske.Yield: 91.3% of theory.
Eksempel 151 6-[4-(N-Acetyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 151 6- [4- (N-Acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 143 ud fra 6-(4-phenylsulfoximino-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- (4-phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 112-114°C.Melting point: 112-114 ° C.
Udbytte: 89,2% af det teoretiske.Yield: 89.2% of theory.
25 Eksempel 152 6-[4-(4-Chlor-N-acetyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 152 6- [4- (4-Chloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-chlor-phenylsulfoximino)-butoxy]-4,4-dimethyl-30 4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-chloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 120-122°C.Melting point: 120-122 ° C.
Udbytte: 86,9% af det teoretiske.Yield: 86.9% of theory.
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Eksempel 153 6-[4- (4-Methyl-N-acetyl-phenylsulfoximino) -butoxy] -4,4-di-nrhexyl-4H-3,l-benzoxazin-2-on.Example 153 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-di-hexhexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[4-(4-methyl-phenylsulfoximino)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Olie, RF-værdi: 0,4 (kiselgelplade: chloroform/acetone = 9:1).Oil, RF value: 0.4 (silica gel plate: chloroform / acetone = 9: 1).
Udbytte: 98,9% af det teoretiske.Yield: 98.9% of theory.
10 c33H48N205S (584,82)C33H48N205S (584.82)
Beregnet: C 67,78 H 8,27 S 5,48Calculated: C 67.78 H 8.27 S 5.48
Fundet : 67,89 8,31 5,60Found: 67.89 8.31 5.60
Eksempel 154 6-[4-(4-Cyclohexyl-N-acetyl-phenylsulfoximino)-butoxy]-15 4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 154 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -15,4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-cyclohexyl-phenylsulfoximino)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 134-136°C.Melting point: 134-136 ° C.
20 Udbytte: 81,9% af det teoretiske.Yield: 81.9% of theory.
Eksempel 155 6-[4-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-butoxy]- 4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 155 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 25 6-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Olie, RF-værdi: 0,54 (kiselgelplade: chloroform/acetone= 9:1) .Oil, RF value: 0.54 (silica gel plate: chloroform / acetone = 9: 1).
Udbytte: 68,8% af det teoretiske.Yield: 68.8% of theory.
30 C32H44C12N2°5S (639,70)C32H44C12N2 ° 5S (639.70)
Beregnet: C 60,08 H 6,93 Cl 11,08 s 5,01Calculated: C 60.08 H 6.93 Cl 11.08 s 5.01
Fundet : 59,87 7,13 11,20 4,95Found: 59.87 7.13 11.20 4.95
DK 164860 BDK 164860 B
9494
Eksempel 156 6- [4- (4-Acetamido-N-acetyl-phenylsulfoximino) -butoxy] - 4.4- di-n-hexyl-4H-3,l-benzoxazin-2-on.Example 156 6- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[4-(4-acetamido-phenylsulfoximino)-butoxy]-4,4-di-n-hexyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 6- [4- (4-acetamido-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 122-124°C.Melting point: 122-124 ° C.
Udbytte: 83,6% af det teoretiske.Yield: 83.6% of theory.
Eksempel 157 10 6-[4-(4-Acetamido-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dicyclohexyl-4H-3,l-benzoxazin-2-on.Example 157 6- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 43 ud fra 6-[4-(4-acetamido-phenylsulfoximino)-butoxy]-4,4-di-cyclohecyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 43 from 6- [4- (4-acetamido-phenylsulfoximino) -butoxy] -4,4-di-cyclohecyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Smeltepunkt: 146°C (sønderdeling).Melting point: 146 ° C (dec.).
Udbytte: 78,3% af det teoretiske.Yield: 78.3% of theory.
Eksempel 158 6-[4-(4-Methyl-N-acetyl-phenylsulfoximino)-butoxy]-4,4-dicyclohexyl-4H-3,l-benzoxazin-2-on.Example 158 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 143 ud fra 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -4,4-dicyclo-hexyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 148-149°C.Melting point: 148-149 ° C.
Udbytte: 78,9% af det teoretiske.Yield: 78.9% of theory.
25 Eksempel 159 6- [4- (4-Acetamido-N-acetyl-phenylsulfoximino) -butoxy] -4H-3,l-benzoxazin-2-on.Example 159 6- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-acetamido-phenylsulfoximino)-butoxy]-4H-3,1-30 benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-acetamido-phenylsulfoximino) -butoxy] -4H-3,1 -30-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 200-201°C.Melting point: 200-201 ° C.
Udbytte: 73,7% af det teoretiske.Yield: 73.7% of theory.
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Eksempel 160 6- [4-(4-Methyl-N-acetyl-phenylsulfoximino)-butoxy]-4H- 3,l-benzoxazin-2-on.Example 160 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[4-(4-methyl-phenylsulfoximino)-butoxy]-4H-3,1-benz-oxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -4H-3,1-benz-oxazin-2-one and acetanhydride.
Olie, RF-værdi: 0,62 (kiselgelplade: chloroform/eddike-syreethylester = 9:1).Oil, RF value: 0.62 (silica gel plate: chloroform / acetic acid ethyl ester = 9: 1).
Udbytte: 45% af det teoretiske.Yield: 45% of theory.
10 Eksempel 161 6-[4-(4-Cyclohexyl-N-acetyl-phenylsulfoximino)-butoxy]-4H-3,l-benzoxazin-2-on.Example 161 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-cyclohexyl-phenylsulfoximino)-butoxy]-4H-3,1-15 benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-cyclohexyl-phenylsulfoximino) -butoxy] -4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 124-125°c.Melting point: 124-125 ° C.
Udbytte: 86,8% af det teoretiske.Yield: 86.8% of theory.
Eksempel 162 6-[4-(4-Cyclohexyl-N-acetyl-phenylsulfoximino)-butoxy]-20 4,4-dicyclohexyl-4H-3,l-benzoxazin-2-on.Example 162 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -20 4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-cyclohexyl-phenylsulfoximino)-butoxy]-4,4-di-cyclohexyl-4H-3,l-benzoxazin-2-on og acetanhydrid. Smeltepunkt: 130°C.Prepared analogously to Example 143 from 6- [4- (4-cyclohexyl-phenylsulfoximino) -butoxy] -4,4-di-cyclohexyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 130 ° C.
25 Udbytte: 70,2% af det teoretiske.Yield: 70.2% of theory.
Eksempel 163 6-[5-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-pentoxy]- 4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 163 6- [5- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 30 6-[5-(3,4-dichlor-phenylsulfoximino)-pentoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [5- (3,4-dichloro-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 126-128°C.Melting point: 126-128 ° C.
Udbytte: 50,6% af det teoretiske.Yield: 50.6% of theory.
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Eksempel 164 6-15-- (4-Cyclohexyl-N-acetyl-phenylsulfoximino) -pentoxy] -4 ,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 164 6-15-- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[5-(4-cyclohexyl-phenylsulfoximino)-pentoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5- [5- (4-cyclohexyl-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 95-96°C.Melting point: 95-96 ° C.
Udbytte: 83,5% af det teoretiske.Yield: 83.5% of theory.
Eksempel 165 10 6-[3-(4-Cyclohexyl-N-acetyl-phenylsulfoximino)-propoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 165 6- [3- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[3-(4-cyclohexyl-phenylsulfoximino)-propoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [3- (4-cyclohexyl-phenylsulfoxymino) -propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Smeltepunkt: 114-115°C.Melting point: 114-115 ° C.
Udbytte: 94,2% af det teoretiske.Yield: 94.2% of theory.
Eksempel 166 6-[3-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-propoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 166 6- [3- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 143 ud fra 6-[3-(3,4-dichlor-phenylsulfoximino)-propoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [3- (3,4-dichloro-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 198-200°C.Melting point: 198-200 ° C.
Udbytte: 81,2% af det teoretiske.Yield: 81.2% of theory.
25 Eksempel 167 6-[2-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-ethoxy] - 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 167 6- [2- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[2-(3,4-dichlor-phenylsulfoximino)-ethoxy]-4,4-dime-30 thyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [2- (3,4-dichloro-phenylsulfoxymino) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 154-155°C.Melting point: 154-155 ° C.
Udbytte: 81,2% af det teoretiske.Yield: 81.2% of theory.
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Eksempel 168 6-[4-(3,4-Dimethyl-phenylsulfinyl)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 168 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-[4-(3,4-dimethyl-phenylmercapto)-butoxy]-4,4-dime- thyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 131-132°C.Melting point: 131-132 ° C.
Udbytte: 83,3% af det teoretiske.Yield: 83.3% of theory.
Eksempel 169 10 6-[6-(3,4-Dichlor-phenylsulfinyl)-hexyloxy]-4,4-dime- thyl-4H-3,l-benzoxazin-2-on.Example 169 6- [6- (3,4-Dichloro-phenylsulfinyl) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[6-(3,4-dichlor-phenylmercapto)-hexyloxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [6- (3,4-dichloro-phenylmercapto) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 156-158°C.Melting point: 156-158 ° C.
Udbytte: 71,5% af det teoretiske.Yield: 71.5% of theory.
Eksempel 170 6-[6-(3,4-Dimethoxy-phenylsulfonyl)-hexyloxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 170 6- [6- (3,4-Dimethoxy-phenylsulfonyl) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[6-(3,4-dimethoxy-phenylmercapto)-hexyloxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [6- (3,4-dimethoxy-phenylmercapto) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 131-132°C.Melting point: 131-132 ° C.
Udbytte: 61,0% af det teoretiske.Yield: 61.0% of theory.
25 Eksempel 171 6-[4-(3,4-Dimethyl-N-acetyl-phenylsulfoximino)-butoxy]-4H-3,l-benzoxazin-2-on.Example 171 6- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(3,4-dimethyl-phenylsulfoximino)-butoxt]-4H-3,Ι-ΙΟ benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (3,4-dimethyl-phenylsulfoximino) -butox] -4H-3, Ι-ΙΟ benzoxazin-2-one and acetanhydride.
Harpiks, RF-værdi: 0,7 (kiselgelplade: chloroform/etha-nol = 9:1).Resin, RF value: 0.7 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte 90,2% af det teoretiske.Yield 90.2% of theory.
C22H26N2°5S (430,53) 35 Beregnet: C 61,38 H 6,09 N 6,51 S 7,45 98C22H26N2 ° 5S (430.53) Calculated: C 61.38 H 6.09 N 6.51 S 7.45 98
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Fundet: C 61,79 H 6,32 N 6,24 S 7,38Found: C 61.79 H 6.32 N 6.24 S 7.38
Eksempel 172 6-[-(3,4-Dimethyl-N-acetyl-phenylsulfoximino)-butoxy]- 4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 172 6 - [- (3,4-Dimethyl-N-acetyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 143 ud fra 6-[4-(3,4-dimethyl-phenylsulfoximino)-butoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on-acetanhydrid.Prepared analogously to Example 143 from 6- [4- (3,4-dimethyl-phenylsulfoxymino) -butoxy) -4,4-dimethyl-4H-3,1-benzoxazine-2-one acetate anhydride.
Smeltepunkt: 14 6°C.Melting point: 14 6 ° C.
Udbytte: 86,5% af det teoretiske.Yield: 86.5% of theory.
10 Eksempel 173 6-[6-(3,4-Dimethoxy-phenylsulfoximino)-hexyloxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 173 6- [6- (3,4-Dimethoxy-phenylsulfoxymino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[6-(3,4-dimethoxy-phenylsulfinyl)-hexyloxy]-4,4-15 dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [6- (3,4-dimethoxy-phenylsulfinyl) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one ethyl ester.
Smeltepunkt: 108-109°C.Melting point: 108-109 ° C.
Udbytte: 83,9% af det teoretiske.Yield: 83.9% of theory.
Eksempel 174 20 6-[3-(3,4-Dichlor-phenylmercapto)-propxy]-4,4-isopro-pyl-4H-3,l-benzoxazin-2-on.Example 174 6- [3- (3,4-Dichloro-phenylmercapto) propoxy] -4,4-isopropyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(3-chlorpropoxy)-4-isopropyl-4H-3,l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 6- (3-chloropropoxy) -4-isopropyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
25 Smeltepunkt: 109-111°C.Melting point: 109-111 ° C.
Udbytte: 75,7% af det teoretiske.Yield: 75.7% of theory.
Eksempel 175 4-Isopropyl-6-[3-(3,4-dimethoxy-phenylmercapto)-propoxy]-4H-3,l-benzoxazin-2-on.Example 175 4-Isopropyl-6- [3- (3,4-dimethoxy-phenylmercapto) -propoxy] -4H-3,1-benzoxazin-2-one.
30 Fremstillet analogt med eksempel 1 ud fra 6-(3-chlorpropoxy)-4-isopropyl-4H-3,l-benzoxazin-2-on og 3,4-dimethoxy-thiophenol.Prepared analogously to Example 1 from 6- (3-chloropropoxy) -4-isopropyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.
Smeltepunkt: 102-103°C.Melting point: 102-103 ° C.
Udbytte: 84,2% af det teoretiske.Yield: 84.2% of theory.
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Eksempel 176 6-[4- (3,4-Dichlor-N-acetyl-phenylsulfoximino)-butoxy]- 4-ethyl-4H-3,l-benzoxazin-2-on.Example 176 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4-ethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[4- (3,4-dichlor-phenylsulfoximino)-butoxy]-4-ethyl- 4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4-ethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 156-158°C.Melting point: 156-158 ° C.
Udbytte: 87,31 af det teoretiske.Yield: 87.31 of theory.
Eksempel 177 10 6- [3- (3,4-Dichlor-phenylsulfinyl)-propoxy]-4-isopropyl- 4H-3,l-benzoxazin-2-on.Example 177 6- [3- (3,4-Dichloro-phenylsulfinyl) propoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[3- (3,4-dichlor-phenylmercapto)-propoxy]-4-isopropyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [3- (3,4-dichloro-phenylmercapto) propoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 58-60°C.Melting point: 58-60 ° C.
Udbytte: 83,3% af det teoretiske.Yield: 83.3% of theory.
Eksempel 178 6- [3- (3,4-Dimethoxy-phenylsulfinyl)-propoxy]-4-iso-propyl-4H-3,l-benzoxazin-2-on.Example 178 6- [3- (3,4-Dimethoxy-phenylsulfinyl) -propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6- [3- (3,4-dimethoxy-phenylmercapto)-propoxy]-4-iso-propyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [3- (3,4-dimethoxy-phenylmercapto) -propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 5 8-6 0 °C.Melting point: 5-8 ° C.
Udbytte: 91,1% af det teoretiske.Yield: 91.1% of theory.
25 _ Eksempel 179 6- [6- (3,4-Dichlor-N-acetyl-phenylsulfoximino)-hexyloxy]- 4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 179 6- [6- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 43 ud fra 6- [6- (3,4-dichlor-phenylsulfoximino)-hexyloxy]-4,4-30 dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 43 from 6- [6- (3,4-dichloro-phenylsulfoximino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Olie, RF-værdi: 0,64 (kiselgelplade: chloroform/ethanol= 9:1) .Oil, RF value: 0.64 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 83,1% af det teoretiske.Yield: 83.1% of theory.
C24H28C12H2°5S (527'48> 35 Beregnet: C 54,65 H 5,35 S 6,08C24H28C12H2 ° 5S (527'48> 35 Calc'd: C 54.65 H 5.35 S 6.08
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Fundet: C 54,30 H 5,34 S 6,06Found: C 54.30 H 5.34 S 6.06
Eksempel 180 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4-isopro-pyl-4H-3,l-benzoxazin-2-on.Example 180 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4-isopropyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one and O ethyl ester.
Smeltepunkt: 123-125°C.Melting point: 123-125 ° C.
10 Udbytte: 47,7% af det teoretiske.Yield: 47.7% of theory.
Eksempel 181 6—[6—(3,4-Dimethoxy-N-acetyl-phenylsulfoximino)-hexyl-oxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 181 6- [6- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -hexyl-oxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 15 6-[6-(3,4-dimethoxy-phenylsulfoximino)-hexyloxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [6- (3,4-dimethoxy-phenylsulfoxymino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Olie, RF-værdi: 0,65 (kiselgelplade: chloroform/etha-nol = 9:1).Oil, RF value: 0.65 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 83,5% af det teoretiske.Yield: 83.5% of theory.
20 C26H34N207S (518,63)C26H34N2O7S (518.63)
Beregnet: C 60,21 H 6,61 S 6,18C, 60.21; H, 6.61; S, 6.18
Fundet : 59,90 6,59 6,13Found: 59.90 6.59 6.13
Eksempel 182 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4,4-di-25 methyl-4H-3,l-benzoxazin-2-on.Example 182 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
3,3 g (0,0075 mol) 6-[4-(3,4-dichlor-phenylsulf inyl) -butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on indrørtes ved 45°C i 50 ml polyphosphorsyre. Efter at praktisk taget alt var opløst,sattes der indenfor 30 30 minutter 0,65 g (0,01 mol) natriumazid til i små portioner. Der bemærkedes en svag nitrogengasudvikling.3.3 g (0.0075 mol) of 6- [4- (3,4-dichloro-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was stirred at 45 °. C in 50 ml polyphosphoric acid. After practically everything dissolved, 0.65 g (0.01 mole) of sodium azide was added in small portions within 30 minutes. Weak nitrogen gas evolution was noted.
Den beigefarvede, cremeagtige skummede masse omrørtes i 3 timer ved 45-50°C og tilsattes 150 g is. Den opståede uklare opløsning indstilledes med koncentreret ammo-35 niak til pH 8 og det harpiksagtige produkt ekstraheredesThe beige creamy foamy mass was stirred for 3 hours at 45-50 ° C and 150 g of ice was added. The resulting cloudy solution was adjusted to pH 8 with concentrated ammonia and the resinous product extracted
LI IV I DH-ODU DLI IV I DH-ODU D
101 med chloroform. Den olieagtige inddampningsrest omkrystalliseredes i eddikesyreethylester/diisopropylether.101 with chloroform. The oily residue was recrystallized from acetic acid ethyl ester / diisopropyl ether.
Der opnåedes hvide krystaller.White crystals were obtained.
Smeltepunkt: 166-167°C.Melting point: 166-167 ° C.
5 Udbytte: 2,0 g (58,6% af det teoretiske).Yield: 2.0 g (58.6% of theory).
Eksempel 183 6-[4-(3,4-Dichlor-phenylsulf imino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 183 6- [4- (3,4-Dichloro-phenylsulfinamino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-10 (3,4-dichlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H- 3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-syre-ethylester.Prepared analogously to Example 6 from 6- [4-10 (3,4-dichloro-phenylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O acid ethyl ester.
Smeltepunkt: 165-166°C.Melting point: 165-166 ° C.
Udbytte: 10% af det teoretiske.Yield: 10% of theory.
15 Eksempel 184 6-[3-(3,4-Dimethoxy-phenylsulfoximino)-propoxy]-4-iso-propyl-4H-3,l-benzoxazin-2-on.Example 184 6- [3- (3,4-Dimethoxy-phenylsulfoxymino) -propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[3-(3,4-dimethoxy-phenylsulfinyl)-propoxy]-4-isopropyl-4H-20 3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-syre-ethylester.Prepared analogously to Example 6 from 6- [3- (3,4-dimethoxy-phenylsulfinyl) -propoxy] -4-isopropyl-4H-20,1-benzoxazin-2-one ethyl ester.
Smeltepunkt: 123-125°C.Melting point: 123-125 ° C.
Udbytte: 77,3% af det teoretiske.Yield: 77.3% of theory.
Eksempel 185 25 6-[4-(3,4-Dichlor-N-p-toluensulfonyl-phenylsulfimino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 185 6- [4- (3,4-Dichloro-N-p-toluenesulfonyl-phenylsulfimino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
4,26 g (0,01 mol) 6-[4-(3,4-dichlor-phenylmercapto) -butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on suspenderedes i 50 ml methanol og tilsattes så meget chloro-30 form, at der fremkom en klar opløsning (ca. 80 ml). Hertil sattes under omrøring en opløsning af 3,38 g (0,012 mol) N-chlor-p-toluensulfonsyreamid-natriumsalt i 30 ml methanol,og blandingen henstilledes i 4 timer ved stuetemperatur. Til den gule reaktionsopløsning sattes ca.4.26 g (0.01 mole) of 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one were suspended in 50 ml of methanol. and added so much chloroform that a clear solution (about 80 ml) was obtained. To this was added a solution of 3.38 g (0.012 mol) of N-chloro-p-toluenesulfonic acid sodium salt in 30 ml of methanol and the mixture was allowed to stand for 4 hours at room temperature. To the yellow reaction solution was added ca.
35 1 ml iseddikesyre, og opløsningsmidlet afdestilleredes 10235 ml of glacial acetic acid and the solvent were distilled off 102
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i en rotationsfordamper (badtemperatur: <20°C). Den lysebrune, seje rest rensedes på en kiselgelsøjle (elue-ringsmiddel: eddikesyreethylester/cyclohexan 4:1). De samlede fraktioner reduceredes i en rotationsfordamper 5 til tørhed, og resten omkrystalliseredes en gang i eddi-kesyreethylester/isopropanol.in a rotary evaporator (bath temperature: <20 ° C). The light brown cool residue was purified on a silica gel column (eluent: acetic acid ethyl ester / cyclohexane 4: 1). The combined fractions were reduced in a rotary evaporator 5 to dryness and the residue was recrystallized once in acetic acid ethyl ester / isopropanol.
Smeltepunkt: 162-163°C.Melting point: 162-163 ° C.
Udbytte: 2,0 g (33,6% af det teoretiske).Yield: 2.0 g (33.6% of theory).
Eksempel 186 10 6-[4-(3,4-Dichlor-N-p-toluensulfonyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 186 6- [4- (3,4-Dichloro-N-p-toluenesulfonyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
0,6 g (0,001 mol) 6-[4-(3,4-dichlor-N-p-toluen-sulfonyl-phenylsulfimino)-butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on suspenderedes i 10 ml methanol, til-15 sattes 1 ml 2n natronlud samt 0,2 ml (0,002 mol) 30%'ig hydrogenperoxid og kogtes i 8 timer under tilbagesvaling. Herved fremstod en klar opløsning, der efter reaktionens afslutning reduceredes til tørhed. Resten rensedes på en kiselgelsøjle (chloroform). De samlede fraktioner 20 reduceredes og omkrystalliseredes en gang i ethanol. Smeltepunkt: 174-175°C.0.6 g (0.001 mol) of 6- [4- (3,4-dichloro-Nβ-toluene-sulfonyl-phenylsulfimino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was suspended. in 10 ml of methanol, 1 ml of 2N sodium hydroxide solution and 0.2 ml (0.002 mol) of 30% hydrogen peroxide were added and refluxed for 8 hours. Thereby a clear solution appeared which, after completion of the reaction, was reduced to dryness. The residue was purified on a silica gel column (chloroform). The total fractions 20 were reduced and recrystallized once in ethanol. Melting point: 174-175 ° C.
Udbytte: 0,27 g (44,1% af det teoretiske).Yield: 0.27 g (44.1% of theory).
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Eksempel 187 6-[3-(3,4-Dichlor-phenylsulfoximino)-propoxy]-4-iso-propyl-4H-3,l-benzoxazin-2-on.Example 187 6- [3- (3,4-Dichloro-phenylsulfoximino) propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 5 6-[3-(3,4-dichlor-phenylsulfinyl)-propoxy]-4-isopropyl- 4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 5 6- [3- (3,4-dichloro-phenylsulfinyl) propoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acetate hydroxamic acid ethyl ester.
Harpiks, RF.værdi: 0,45 (kiselgelplade: chloroform/etha-nol = 19:1).Resin, RF value: 0.45 (silica gel plate: chloroform / ethanol = 19: 1).
10 Udbytte: 43,7% af det toeretiske.Yield: 43.7% of tertiary ethics.
C20H22C12N2°2S (457,38)C20H22C12N2 ° 2S (457.38)
Beregnet: C 52,52 H 4,85 S 7,01Calculated: C 52.52 H 4.85 S 7.01
Fundet : 52,49 5,12 6,63Found: 52.49 5.12 6.63
Eksempel 188 15 6-[3-(3,4-Dimethoxy-N-acetyl-phenylsulfoximino)-propoxy ]- 4-isopropyl~4H-3,l-benzoxazin-2-on.Example 188 6- [3- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) propoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[3-(3,4-dimethoxy-phenylsulfoximino)-propoxy]-4-iso-propyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [3- (3,4-dimethoxy-phenylsulfoxymino) -propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one and acetanhydride.
20 Smeltepunkt: 73-75°C.Melting point: 73-75 ° C.
Udbytte: 81,4% af det teoretiske.Yield: 81.4% of theory.
Eksempel 189 6-[4-(4-Cyclohexyl-phenylmercapto)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 189 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 1 ud fra 6-(4-cyclobutoxy)-4,4-diethyl-4H-3,l-benzoxazin-2-on og 4-cyclohexyl-thiophenol.Prepared analogously to Example 1 from 6- (4-cyclobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and 4-cyclohexyl-thiophenol.
Smeltepunkt: 85-88°C.Melting point: 85-88 ° C.
Udbytte: 69,1% af det teoretiske.Yield: 69.1% of theory.
30 Eksempel 190 6-[4-(3,4-Dichlor-phenylmercapto)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 190 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-diethyl-4H-3,l-benzoxazin-2-on 35 og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one 35 and 3,4-dichloro-thiophenol.
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Smeltepunkt: 143-145°C.Melting point: 143-145 ° C.
Udbytte: 58,7% af det teoretiske.Yield: 58.7% of theory.
Eksempel 191 6-(4-Phenylmercapto-butoxy)-4,4-diethyl-4H-3,1-benz-5 oxazin-2-on.Example 191 6- (4-Phenylmercapto-butoxy) -4,4-diethyl-4H-3,1-benz-5-oxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-diethyl-4H-3,l-benzoxazin-2-on og thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and thiophenol.
Smeltepunkt: 104-106°C.Melting point: 104-106 ° C.
10 Udbytte: 69,8% af det teoretiske.Yield: 69.8% of theory.
Eksempel 192 6-[4-(3,4-Dimethyl-phenylmercapto)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 192 6- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 15 6-(4-chlorbutoxy)-4,4-diethyl-4H-3,l-benzoxazin-2-on og 3,4-dimethyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethylthiophenol.
Smeltepunkt: 124-125°C.Melting point: 124-125 ° C.
Udbytte: 83,4% af det teoretiske.Yield: 83.4% of theory.
Eksempel 193 20 6-[4-(3,4-Dimethoxy-phenylmercapto)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 193 6- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-diethyl-4H-3,l-benzoxazin-2-on og 3,4-dimethoxy-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.
25 Smeltepunkt: 110-111°C.Melting point: 110-111 ° C.
Udbytte: 72,6% af det teoretiske.Yield: 72.6% of theory.
Eksempel 194 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 194 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
30 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-diethyl-4H-3,l-benzoxazin-2-on og 4-acetamido-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.
Smeltepunkt: 90-9 2°C.Melting point: 90-9 2 ° C.
Udbytte: 62,9% af det teoretiske.Yield: 62.9% of theory.
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Eksempel 195 6-[4-(3,4-Dichlor-phenylmercapto)-butoxy]-4-methyl-4H- 3.1- benzoxazin-2-on.Example 195 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4-methyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4-methyl-4H-3,l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4-methyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 117-119°C.Melting point: 117-119 ° C.
Udby-te: 50,5% af det teoretiske.Yield: 50.5% of theory.
Eksempel 196 10 6-[4-(4-Methyl-phenylmercapto)-butoxy]-4-methyl-4H-3,1-benzoxazin-2-on.Example 196 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4-methyl-4H-3,l-benzoxazin-2-on og 4-methyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4-methyl-4H-3,1-benzoxazin-2-one and 4-methylthiophenol.
15 Smeltepunkt: 111-113°C.Melting point: 111-113 ° C.
Udbytte: 54,4% af det teoretiske.Yield: 54.4% of theory.
Eksempel 197 6-[4-(4-Acetamido-phenylmercapto)-butoxy]-4-methyl-4H- 3.1- benzoxazin-2-on.Example 197 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4-methyl-4H-3.1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4-methyl-4H-3,l-benzoxazin-2-on og 4-acetamido-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4-methyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.
Smeltepunkt: 122-124°C.Melting point: 122-124 ° C.
Udbytte: 44,2% af det teoretiske.Yield: 44.2% of theory.
25 Eksempel 198 6-[4-(2-Benzthiazolylmercapto)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on.Example 198 6- [4- (2-Benzthiazolylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel lud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 2-mercapto-benzthiazol.Prepared analogously to Example lye from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 2-mercapto-benzthiazole.
Smeltepunkt: 183-184^(3.Melting point: 183-184
Udbytte: 56,3% af det teoretiske.Yield: 56.3% of theory.
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Eksempel 199 6-[4-(4,6-Dimethyl-2-pyrimidinylmercapto)-butoxy]-4,4-d imethy1-4H-3,l-benzoxaz in-2-on.Example 199 6- [4- (4,6-Dimethyl-2-pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4,6-dimethyl-2-mercaptopyrimidin.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4,6-dimethyl-2-mercaptopyrimidine.
Smeltepunkt: 125-127°C.Melting point: 125-127 ° C.
Udbytte: 65,9% af det teoretiske.Yield: 65.9% of theory.
Eksempel 200 10 6- [4- (l-Oxido-2-pyridylmercapto) -butoxy] -4,4-dimethyl- 4H-3,l-benzoxazin-2-on.Example 200 6- [4- (1-Oxido-2-pyridylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 2-mercapto-pyridin-l-oxid.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 2-mercapto-pyridine-1-oxide.
15 Smeltepunkt: 154-156°C.Melting point: 154-156 ° C.
Udbytte: 14,6% af det teoretiske.Yield: 14.6% of theory.
Eksempel 201 6-[4-(1,2,4-Triazol-3-yl-mercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 201 6- [4- (1,2,4-Triazol-3-yl-mercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3-mercapto-l,2,4-triaz0l.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3-mercapto-1,2,4-triazole.
Smeltepunkt: 181-183°C.Melting point: 181-183 ° C.
Udbytte: 42,2% åf det teoretiske 25 Eksempel 202 6- [4- (2-Pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H- 3,l-benzoxazin-2-on.Yield: 42.2% of theoretical Example 202 6- [4- (2-Pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 2-mercapto-pyrimidin.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 2-mercapto-pyrimidine.
Smeltepunkt: 142-144°C.Melting point: 142-144 ° C.
Udbytte: 53,9% af det teoretiske.Yield: 53.9% of theory.
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Eksempel 203 6- [4-(4-Pyridylmercapto)-butoxy]-4,4-dimethyl-4H-3,1-benzoxaz in-2-on.Example 203 6- [4- (4-Pyridylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6- (4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-mercapto-pyridin.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-mercapto-pyridine.
Smeltepunkt: 153-155°C.Melting point: 153-155 ° C.
Udbytte: 64,2% af det teoretiske.Yield: 64.2% of theory.
Eksempel 204 10 8-[4-(4-Cyclohexyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H.3,l-benzoxazin-2-on.Example 204 8- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H.3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 8-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-cyclohexyl-thiophenol.Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.
15 Smeltepunkt: 109-110°CMelting point: 109-110 ° C
Udbytte: 70,5% af det teoretiske.Yield: 70.5% of theory.
Eksempel 205 8- [4-(3,4-Dichlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 205 8- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 8-(4- chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 137-138°C.Melting point: 137-138 ° C.
Udbytte: 74,5% af det teoretiske.Yield: 74.5% of theory.
25 Eksempel 206 8-(4-Phenylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 206 8- (4-Phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 8-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og thiophenol.Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and thiophenol.
Smeltepunkt: 98-100°C.Melting point: 98-100 ° C.
Udbytte: 87,9% af det teoretiske.Yield: 87.9% of theory.
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Eksempel 207 8-[4-(3,4-Dimethyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 207 8- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 8-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dimethyl-thiophenol.Prepared analogously to Example 1 from 5 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethylthiophenol.
Smeltepunkt: 137-139°C.Melting point: 137-139 ° C.
Udbytte: 90,7% af det teoretiske.Yield: 90.7% of theory.
Eksempel 208 10 8- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl- 4H-3,l-benzoxazin-2-on.Example 208 8- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 8-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dimethoxy-thiophenol.Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.
15 Smeltepunkt: 116-117°C.Melting point: 116-117 ° C.
Udbytte: 93,8% af det teoretiske.Yield: 93.8% of theory.
Eksempel 209 8-[4-(4-Acetamido-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 209 8- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 8-(4-chlorbutoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-acetamido-thiophenol.Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.
Smeltepunkt: 166-167°Ci Udbytte: 63,6% af det teoretiske.Melting point: 166-167 ° C Yield: 63.6% of theory.
25 Eksempel 210 6-[4-(3,4-Dimethylphenyimercapto)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 210 6- [4- (3,4-Dimethylphenylimercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
9,1 g (0,0234 mol) 6-(4-methansulfonyloxy-butoxy)-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 3,5 g (0,025 mol) 3,4-dimethyl-thiophenol opløses i 80 ml dimethylformamid. Under omrøring tilsættes der 6,9 g (0,05 mol) kaliumcarbonat og til sidst 4 ml vand. Reaktionsblandingen bliver kortvarigt varm, og efter at varmetoningen er døet hen, omrøres den i 35 endnu 2 timer ved stuetemperatur. Efter tilsætning af 1099.1 g (0.0234 mole) of 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3.5 g (0.025 mole) ) 3,4-Dimethyl-thiophenol is dissolved in 80 ml of dimethylformamide. With stirring, 6.9 g (0.05 mole) of potassium carbonate and finally 4 ml of water are added. The reaction mixture becomes briefly warm and after the heat mixture has died, it is stirred for another 2 hours at room temperature. After the addition of 109
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isvand esktraherer man med chloroform, vasker den organiske fase med vand, tørrer med natriumsulfat og afdestillerer opløsningsmidlet i vakuum. Remanensen renses over en kiselgelsøjle (elueringsmiddel: chloro-5 form/ethanol = 40:1).ice water is extracted with chloroform, the organic phase is washed with water, dried with sodium sulfate and the solvent is distilled off in vacuo. The residue is purified over a silica gel column (eluent: chloroform / ethanol = 40: 1).
Olie, RF-værdi: 0,4 (kiselgelplade: chloroform/ethanol = 9:1) .Oil, RF value: 0.4 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 7,6 g (75,4% af det teoretiske).Yield: 7.6 g (75.4% of theory).
C22H26N2°5S (430,52) 10 Beregnet: C 61,38 H 6,09 N 6,51 S 7,45C22H26N2 ° 5S (430.52) Calculated: C 61.38 H 6.09 N 6.51 S 7.45
Fundet : 61,10 6,07 6,24 7,28Found: 61.10 6.07 6.24 7.28
Eksempel 211 6-[4-(4-Acetamido-phenylmercapto)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 211 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
15 Fremstillet analogt med eksempel 210 ud fra 6-(4-methansulfonyloxy-butoxy)-7-nitro-4,4-dimethyl-4H- 3,l-benzoxazin-2-on og 4-acetamido-thiophenol.Prepared analogously to Example 210 from 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.
Smeltepunkt: 203-205°C.Melting point: 203-205 ° C.
Udbytte: 69,2% af det teoretiske.Yield: 69.2% of theory.
20 Eksempel 212 6-[4-(4-Chlor-phenylmercapto)-butoxy]-7-nitro-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 212 6- [4- (4-Chloro-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 6-(4-methansulfonyloxy-butoxy)-7-nitro-4,4-dimethyl-25 4H-3,l-benzoxazin-2-on og 4-chlor-thiophenol.Prepared analogously to Example 210 from 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-chloro-thiophenol.
Smeltepunkt: 155-156°C.Melting point: 155-156 ° C.
Udbytte: 69,5% af det teoretiske.Yield: 69.5% of theory.
Eksempel 213 6-[4-(2-Pyridylmercapto)-butoxy]-7-nitro-4,4-dimethyl-30 4H-3,l-benzoxazin-2-on.Example 213 6- [4- (2-Pyridylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 6-(4-methansulfonyloxy-butoxy)-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 2-mercapto-pyridin.Prepared analogously to Example 210 from 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 2-mercapto-pyridine.
Smeltepunkt: 98-100°C.Melting point: 98-100 ° C.
35 Udbytte: 59,3% af det teoretiske.Yield: 59.3% of theory.
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Eksempel 214 6-[4-(4-Methyl-phenylmercapto)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 214 6- [4- (4-Methyl-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 5 6-(4-methansulfonyloxy-butoxy)-7-nitro-4,4-dimethyl- 4H-3,l-benzoxazin-2-on og 4-methyl-thiophenol.Prepared analogously to Example 210 from 5 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-methyl-thiophenol.
Smeltepunkt: 128-129°C.Melting point: 128-129 ° C.
Udbytte: 77,7% af det teoretiske.Yield: 77.7% of theory.
Eksempel 215 10 6-[4-(3,4-Dimethoxy-phenylmercapto)-butoxy]-7-nitro-4,4- dimethyl-4H-3,l-benzoxazin-2-on.Example 215 6- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 6- (4-methansulfonyloxy-butoxy)-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 3,4-dimethoxy-thiophenol.Prepared analogously to Example 210 from 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.
15 Smeltepunkt: 115-117°C.Melting point: 115-117 ° C.
Udbytte: 82,5% af det teoretiske.Yield: 82.5% of theory.
Eksempel 216 7- [4-(3,4-Dimethyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 216 7- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 210 ud fra 7-(4-methansulfonyloxy-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on og 3f4-dimethyl-thiophenol.Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethyl-thiophenol.
Smeltepunkt: 120-122°C.Melting point: 120-122 ° C.
Udbytte: 84,5% af det teoretiske.Yield: 84.5% of theory.
25 Eksempel 217 7-[4-(4-Acetamido-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 217 7- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 7-(4-methansulfonyloxy-butoxy)-4 f4-dimethyl-4H-3,1-30 benzoxazin-2-on og 4-acetamido-thiophenol.Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4β-dimethyl-4H-3,1 -30-benzoxazin-2-one and 4-acetamido-thiophenol.
Smeltepunkt: 162-164°C.Melting point: 162-164 ° C.
Udbytte: 97,7% af det teoretiske.Yield: 97.7% of theory.
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Eksempel 218 7-[4-(2-Pyridylmercapto)-butoxy]-4,4-dimethyl-4H-3, 1-benzoxa z in-2-on.Example 218 7- [4- (2-Pyridylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 5 7-(4-methansulfonyloxy-butoxy)-4,4-dimethyl-4H-3,1- benzoxazin-2-on og 2-mercaptopyridin.Prepared analogously to Example 210 from 5- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 2-mercaptopyridine.
Smeltepunkt: 125-127°C.Melting point: 125-127 ° C.
Udbytte: 75,4% af det teoretiske.Yield: 75.4% of theory.
Eksempel 219 10 7-[4-(4-Methyl-phenylmercapto)-butoxyJ-4,4-dimethyl- 4H-3,l-benzoxazin-2-on.Example 219 7- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 7-(4-methansulfonyloxy-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on og 4-methyl-thiophenol.Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-methyl-thiophenol.
15 Smeltepunkt: 120-122°C.Melting point: 120-122 ° C.
Udbytte: 80,7% af det teoretiske.Yield: 80.7% of theory.
Eksempel 220 7-[4-(4-Chlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H- 3,l-benzoxazin-2-on.Example 220 7- [4- (4-Chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 210 ud fra 7-(4-methansulfonyloxy-butoxy)-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-chlor-thiophenol.Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-chloro-thiophenol.
Smeltepunkt: 117-119°C.Melting point: 117-119 ° C.
Udbytte: 86,7% af det teoretiske.Yield: 86.7% of theory.
25 Eksempel 221 7-[4-(3,4-Dichlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 221 7- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 7-(4-methansulfonyloxy-butoxy)-4,4-dimethyl-4H-3,1-30 benzoxazin-2-on og 3,4-dichlor-thiophenol.Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.
Smeltepunkt: 104-106°C.Melting point: 104-106 ° C.
Udbytte: 79,7% af det teoretiske.Yield: 79.7% of theory.
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Eksempel 222 7-(4-Phenylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on.Example 222 7- (4-Phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 5 7-(4-methansulfonyloxy-butoxy)-4,4-dimethyl-4H-3,1- benzoxazin-2-on og thiophenol.Prepared analogously to Example 210 from 5- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and thiophenol.
Smeltepunkt: 123-125°C.Melting point: 123-125 ° C.
Udbytte: 89,5% af det teoretiske.Yield: 89.5% of theory.
Eksempie 223 10 7-[4-(3,4-Dimethoxy-phenylmercapto)-butoxy]-4,4-dime- thyl-4H-3 ,l-benzoxazin-2-on.Example 223 7- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 210 ud fra 7-(4-methansulfonyloxy-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on og 3,4-dimethpxy-thiophenol.Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.
15 Olie, RF-værdi: 0,6 (kiselgelplade: ethylenchlorid/ ethanol = 9:1).Oil, RF value: 0.6 (silica gel plate: ethylene chloride / ethanol = 9: 1).
Udbytte: 80,7% af det teoretiske.Yield: 80.7% of theory.
C22H27N05S (417,53)C22H27N05S (417.53)
Beregnet; C 63,29 H 6,52 N 3,35 20 Fundet ; 63,00 6,54 3,38calculated; C 63.29 H 6.52 N 3.35 Found; 63.00 6.54 3.38
Eksempel 224 7-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 224 7- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 25 7-[4-(3,4-dichlor-phenylmercapto)-butoxy]-4,4-dimethyl- 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 7- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt; 8 2-8 4°C.Melting point; 8 ° -8 ° C.
Udbytte: 92,1% af det teoretiske.Yield: 92.1% of theory.
Eksempel 225 30 7-(4-Phenylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz- oxazin-2-on.Example 225 7- (4-Phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 7-(4-phenylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 7- (4-phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and hydrogen peroxide.
35 Smeltepunkt: 117-119°C.Melting point: 117-119 ° C.
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Udbytte: 96,1% af det teoretiske.Yield: 96.1% of theory.
Eksempel 226 7-[4-(3,4-Dimethyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 226 7- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 2 ud fra 7-[4-(3,4-dimethyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin~2-on og hydrogenperoxid.Prepared analogously to Example 2 from 7- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Olie, RF-værdi: 0,6 (kiselgelplade: ethylenchlorid/etha-nol = 9:1).Oil, RF value: 0.6 (silica gel plate: ethylene chloride / ethanol = 9: 1).
10 Udbytte: 95,5% af det teoretiske.Yield: 95.5% of theory.
C22H29N05S (419,54)C22H29N05S (419.54)
Beregnet: C 62,98 H 6,97 N 3,35 S 7,64Calculated: C 62.98 H 6.97 N 3.35 S 7.64
Fundet : 63,24 6,85 3,40 7,64Found: 63.24 6.85 3.40 7.64
Eksempel 227 15 7-[4-(4-Acetamido-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 227 7- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 7-[4-(4-acetamido-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 7- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
20 Smeltepunkt: 145-147°C.Melting point: 145-147 ° C.
Udbytte: 77,8% af det teoretiske.Yield: 77.8% of theory.
Eksempel 228 7-[4-(2-Pyridylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,1-benzoxaz in-2-on.Example 228 7- [4- (2-Pyridylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 2 ud fra 7-[4-(2-pyridylmercapto)-butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 7- [4- (2-pyridylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 153-155°C.Melting point: 153-155 ° C.
Udbytte: 64,9% af det teoretiske.Yield: 64.9% of theory.
30 Eksempel 229 7-[4-(4-Methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3,l-benzoxazin-2-on.Example 229 7- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 7- [ 4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H- 114Prepared analogously to Example 2 from 7- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-114
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3.1- benzoxazin-2-on og hydrogenperoxid.3.1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 128-130°C.Melting point: 128-130 ° C.
Udbytte: 94,4% af det teoretiske.Yield: 94.4% of theory.
Eksempel 230 5 7- [4-(4-Chlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on.Example 230 7- [4- (4-Chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 7-[4-(4-chlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H- 3.1- benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 7- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.
10 Smeltepunkt: 140-142°C.Melting point: 140-142 ° C.
Udbytte: 91,6% af det teoretiske.Yield: 91.6% of theory.
Eksempel 231 7- [4-(3,4-Dimethoxy-phenylsulfinyl)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 231 7- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
15 Fremstillet analogt med eksempel 2 ud fra 7- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4-dime-thyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 7- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Harpiks, RF-værdi: 0,4 (kiselgelplade: ethylenchlorid/ ethanol = 9:1).Resin, RF value: 0.4 (silica gel plate: ethylene chloride / ethanol = 9: 1).
20 Udbytte: 40,8% af det teoretiske.Yield: 40.8% of theory.
C22H27N06S (433,53)C22H27NO6S (433.53)
Beregnet: C 60,95 H 6,28 N 3,23 S 7,40Calculated: C 60.95 H 6.28 N 3.23 S 7.40
Fundet : 60,70 6,25 3,03 7,53Found: 60.70 6.25 3.03 7.53
Eksempel 232 25 8-(4-(4-Cyclohexyl-phenylsulfinyl)-butoxy]-4,4-dimethyl- 4H-3,l-benzoxazin-2-on.Example 232 8- (4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 8- [4-(4-cyclohexyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 8- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
30 Smeltepunkt: 144-145°C.Melting point: 144-145 ° C.
Udbytte: 71,9% af det teoretiske.Yield: 71.9% of theory.
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Eksempel 233 8-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 233 8- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 8-[4-(3,4-dichlorphenylmercapto)-butoxy]-4,4-dimethyl- 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 8- [4- (3,4-dichlorophenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt; 113-114°C.Melting point; 113-114 ° C.
Udbytte: 81,0% af det teoretiske.Yield: 81.0% of theory.
Eksempel 234 10 8- (4-Phenylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz- oxazin-2-on.Example 234 8- (4-Phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 8-(4-phenylmercapto-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 8- (4-phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 162-163°C.Melting point: 162-163 ° C.
Udbytte: 91,6% af det teoretiske.Yield: 91.6% of theory.
Eksempel 235 8-[4-(4-Acetamido-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 235 8- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 8-[4-(4-acetamido-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l~benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 8- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 166-167°C.Melting point: 166-167 ° C.
Udbytte: 63,2% af det teoretiske.Yield: 63.2% of theory.
25 Eksempel 236 8-[4-(3,4-Dimethyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 236 8- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 8-[4-(3,4-dimethyl-phenylmercapto)-butoxy]-4,4-dimethyl-30 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 8- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 111-112°C.Melting point: 111-112 ° C.
Udbytte: 63,9% af det teoretiske.Yield: 63.9% of theory.
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Eksempel 237 8—[4—(3,4-Dimethoxy-phenylsulfinyl)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 237 8- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 8-[4-(3,4-dimethoxy-phenylmercapto)-butoxy]-4,4-dime- thyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 8- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 102-103°C.Melting point: 102-103 ° C.
Udbytte: 90,2% af det teoretiske.Yield: 90.2% of theory.
Eksempel 238 10 6-[4-(4-Cyclohexyl-phenylsulfinyl)-butoxy]-4,4-diethyl- 4H-3,l-benzoxazin-2-on.Example 238 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-cyclohexyl-phenylmercapto)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 168-170°C.Melting point: 168-170 ° C.
Udbytte: 82,7% af det teoretiske.Yield: 82.7% of theory.
Eksempel 239 6- [4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 239 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dichlor-phenylmercapto)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
SmeltepunkT. 91-93°C.Melting point. 91-93 ° C.
Udbytte: 70,9% af det teoretiske.Yield: 70.9% of theory.
25 Eksempel 240 6-(4-Phenylsulfinyl-butoxy)-4,4-diethyl-4H-3,1-benz-oxazin-2-on.Example 240 6- (4-Phenylsulfinyl-butoxy) -4,4-diethyl-4H-3,1-benz-oxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-(4-phenylmercapto-butoxy)-4,4-diethyl-4H-3,1-benz-30 oxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- (4-phenylmercapto-butoxy) -4,4-diethyl-4H-3,1-benz-oxazin-2-one and hydrogen peroxide.
Harpiks, RF-værdi: 0,6 (kiselgelplade: chloroform/etha-nol =9:1).Resin, RF value: 0.6 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 94,3% af det teoretiske.Yield: 94.3% of theory.
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C22H27N04S (401,53)C22H27NO4S (401.53)
Beregnet: C 65,81 H 6,78 N 3,49 S 7,98Calculated: C 65.81 H 6.78 N 3.49 S 7.98
Pundet : 65,55 6,75 3,40 7,71Pound: 65.55 6.75 3.40 7.71
Eksempel 241 5 6-[4-(3,4-Dimethyl-phenylsulfinyl)-butoxy]-4,4-diethyl- 4H-3,l-benzoxazin-2-on.Example 241 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dimethyl-phenylmercapto)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
10 Smeltepunkt: 137-138°C.Melting point: 137-138 ° C.
Udbytte: 83,1% af det teoretiske.Yield: 83.1% of theory.
Eksempel 242 6-[4-(3,4-Dimethoxy-phenylsulfinyl)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 242 6- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
15 Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dimethoxy-phenylmercapto)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 161-163°C.Melting point: 161-163 ° C.
Udbytte: 87,7% af det teoretiske.Yield: 87.7% of theory.
20 Eksempel 243 6-[4-(4-Acetamido-phenylsulfinyl)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 243 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-acetamido-phenylmercapto)-butoxy]-4,4-diethyl-25 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 69-70°C.Melting point: 69-70 ° C.
Udbytte: 92,6% af det teoretiske.Yield: 92.6% of theory.
Eksempel 244 6-[4-(4-Pyridylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,1-30 benzoxazin-2-on.Example 244 6- [4- (4-Pyridylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-pyridylmercapto)-butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-pyridylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 141-143°C.Melting point: 141-143 ° C.
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Udbytte: 36,9% af det teoretiske.Yield: 36.9% of theory.
Eksempel 245 6-[4-(4,6-Dimethyl-2-pyrimidinylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 245 6- [4- (4,6-Dimethyl-2-pyrimidinylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 2 ud fra 6- [4- (4,6-dimethyl-2-pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4,6-dimethyl-2-pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Harpiks, RF-værdi: 0,4 (kiselgelplade: ethylenchlorid/ ethanol = 9:1).Resin, RF value: 0.4 (silica gel plate: ethylene chloride / ethanol = 9: 1).
10 Udbytte: 15,0% af det teoretiske.Yield: 15.0% of theory.
C20H25N3°4S (403,50)C20H25N3 ° 4S (403.50)
Beregnet: C 59,53 H 6,25 S 7,95Calculated: C 59.53 H 6.25 S 7.95
Fundet : 59,30 5,99 7,88Found: 59.30 5.99 7.88
Eksempel 246 15 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4-methyl-4H- 3.1- benzoxazin-2-on.Example 246 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4-methyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dichlor-phenylmercapto)-butoxy]-4-methyl-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4-methyl-3,1-benzoxazin-2-one and hydrogen peroxide.
20 Smeltepunkt: 138-139°C.Melting point: 138-139 ° C.
Udbytte: 86,0% af det teoretiske.Yield: 86.0% of theory.
Eksempel 247 6-[4-(4-Methyl-phenylsulfinyl)-butoxy]-4-methyl-4H-3,1-benzoxazin-2-on.Example 247 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-methyl-phenylmercapto)-butoxy]-4-methyl-4H-3,1-benzoxazin-2-on og hydrogenperoxid·Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide ·
Smeltepunkt: 120-121°C.Melting point: 120-121 ° C.
Udbytte: 58,4% af det teoretiske.Yield: 58.4% of theory.
30 Eksempel 248 6- [4- (4-Acetamido-phenylsulf inyl) -butoxy) -4-methyl-4H- 3.1- benzoxazin-2-on.Example 248 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy) -4-methyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4-methyl-4H- 119Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4-methyl-4H-119
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3,l-benzoxazin-2-on og hydrogenperoxid.3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 124-126°C.Melting point: 124-126 ° C.
Udbytte: 60,4% af det teoretiske.Yield: 60.4% of theory.
Eksempel 249 5 6~[4-(2-Benzthiazolylsulfonyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 249 5- [4- (2-Benzthiazolylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 3 ud fra 6-[4-(2-benzthiazolylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid/iseddikesyre.Prepared analogously to Example 3 from 6- [4- (2-benzthiazolylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide / glacial acetic acid.
10 Smeltepunkt: 177-179°C.Melting point: 177-179 ° C.
Udbytte: 55,9% af det' teoretiske.Yield: 55.9% of theory.
Eksempel 250 6-[4-(1,2,4-Triazolyl-3-sulfonyl)-butoxy]-4, 4-dimethyl-4H-3,l-benzoxazin-2-on.Example 250 6- [4- (1,2,4-Triazolyl-3-sulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
15 Fremstillet analogt med eksempel 3 ud fra 6-[4-(1,2,4-triazolyl-3-mercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid/iseddike. Smeltepunkt: 197-199°C.Prepared analogously to Example 3 from 6- [4- (1,2,4-triazolyl-3-mercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide glacial acetic acid. Melting point: 197-199 ° C.
Udbytte: 83,0% af det teoretiske.Yield: 83.0% of theory.
20 Eksempel 251 6-[4-(2-Pyrimudinylsulfonyl)-butoxy]-4,4-dimethyl-4H- 3,l-benzoxazin-2-on.Example 251 6- [4- (2-Pyrimudinylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 3 ud fra 6-[4-(2-pyrimidinylmercapto)-butoxy]-4,4-dimethyl-4H-25 3,l-benzoxazin-2-on og hydrogenperoxid/iseddike.Prepared analogously to Example 3 from 6- [4- (2-pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-25,1-benzoxazin-2-one and hydrogen peroxide / glacial acetic acid.
Smeltepunkt: 184-186°C.Melting point: 184-186 ° C.
Udbytte: 69,0% af det teoretiske.Yield: 69.0% of theory.
Eksempel 252 5-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-30 4H-3,l-benzoxazin-2-on.Example 252 5- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylsulfinyl)-butylbromid.Prepared analogously to Example 4 from 5-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.
Smeltepunkt: 89-90°C.Melting point: 89-90 ° C.
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Udbytte: 73,2% af det teoretiske.Yield: 73.2% of theory.
Eksempel 253 5-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 253 5- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 6 ud fra 5-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 5- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.
Smeltepunkt: 127-128°C.Melting point: 127-128 ° C.
10 Udbytte: 50% af det teoretiske.Yield: 50% of theory.
Eksempel 254 7- [4- (3,4-Dichlor-phenylsulfoximino) -butoxy] -4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 254 7- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 15 7-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl- 4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 7- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.
Harpiks, RF-værdi: 0,4 (kiselgelplade: ethylenchlorid/ ethanol = 9:1).Resin, RF value: 0.4 (silica gel plate: ethylene chloride / ethanol = 9: 1).
20 Udbytte: 39,2% af det teoretiske.Yield: 39.2% of theory.
C20H22C12N4S (457,39)C20H22C12N4S (457.39)
Beregnet: C 52,52 H 4,85 Cl 15,50 N 6,12 S 7,01Calculated: C 52.52 H 4.85 Cl 15.50 N 6.12 S 7.01
Fundet : 52,34 4,80 15,50 6,16 S 7,01Found: 52.34 4.80 15.50 6.16 S 7.01
Eksempel 255 25 7-[4-(3,4-Dimethyl-phenylsulfoximino)-butoxy]-4,4-dime- thyl-4H-3,l-benzoxazin-2-on.Example 255 7- [4- (3,4-Dimethyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 7- [4- (3,4-dimethyl-phenylsulf inyl) -butoxy] -4,4-dime-thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-30 hydroxamsyre-ethylester.Prepared analogously to Example 6 from 7- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-2-one acet-hydroxamic acid ethyl ester.
Smeltepunkt: 161-163°C.Melting point: 161-163 ° C.
Udbytte: 77,2% af det teoretiske.Yield: 77.2% of theory.
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Eksempel 256 7-[4-(4-Acetamido-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 256 7- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 5 7-[4-(4-acetamido-phenylsulfinyl)-butoxy]-4,4-dimethyl- 4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 5- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one ethyl ester.
Smeltepunkt: 197-198°C.Melting point: 197-198 ° C.
Udbytte: 29,2% af det teoretiske.Yield: 29.2% of theory.
10 Eksempel 257 7-[4-(4-Methyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 257 7- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 7-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-15 4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet- hydroxamsyre-ethylester.Prepared analogously to Example 6 from 7- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet hydroxamic acid. ethyl ester.
Smeltepunkt: 122-124°C.Melting point: 122-124 ° C.
Udbytte: 54,6% af det teoretiske.Yield: 54.6% of theory.
Eksempel 258 20 7-[4-(4-Chlor-phenylsulfoximino)-butoxy]-4,4-dimethyl- 4H-3,l-benzoxazin-2-on.Example 258 20 7- [4- (4-Chloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 7-[4-(4-chlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H- 3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-25 syre-ethylester.Prepared analogously to Example 6 from 7- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 103-105°C.Melting point: 103-105 ° C.
Udbytte: 53,8% af det teoretiske.Yield: 53.8% of theory.
Eksempel 259 7-(4-Phenylsulfoximino-butoxy)-4,4-dimethyl-4H-3,Ι-ΒΟ benzoxazin-2-on.Example 259 7- (4-Phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3, Ι-ΒΟ benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 7-(4-phenylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 7- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
35 Smeltepunkt: 130-132°C.Melting point: 130-132 ° C.
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Udbytte: 75,1% af det teoretiske.Yield: 75.1% of theory.
Eksempel 260 7-[4-(3,4-Dimethoxy-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 260 7- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 6 ud fra 7- [4-(3,4-dimethoxy-phenylsulfinyl)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 7- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.
Smeltepunkt: 110-112°C.Melting point: 110-112 ° C.
10 Udbytte: 81,2% af det teoretiske.Yield: 81.2% of theory.
Eksempel 261 8- [4-(4-Cyclohexyl-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 261 8- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 15 8-[4-(4-cyclohexyl-phenylsulfinyl)-butoxy]-4,4-dime- thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 8- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.
Smeltepunkt: 115-116°C.Melting point: 115-116 ° C.
Udbytte: 47,9% af det teoretiske.Yield: 47.9% of theory.
20 Eksempel 262 8-[4-(3,4-Dimethyl-phenylsulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 262 8- [4- (3,4-Dimethyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 8-[4-(3,4-dimethyl-phenylsulfinyl)-butoxy]-4,4-dime-25 thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester;Prepared analogously to Example 6 from 8- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester;
Smeltepunkt: 130-131°C.Melting point: 130-131 ° C.
Udbytte: 89,6% af det teoretiske.Yield: 89.6% of theory.
Eksempel 263 30 8-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4,4-dime- thyl-4H-3,l-benzoxazin-2-on.Example 263 8- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 8-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet- 123 DK 16486U b hydroxamsyre-ethylester.Prepared analogously to Example 6 from 8- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate DK 16486U b hydroxamic acid ethyl ester.
Smeltepunkt: 144-145°C.Melting point: 144-145 ° C.
Udbytte: 59,6% af det teoretiske.Yield: 59.6% of theory.
Eksempel 264 5 8-(4-Phenylsulfoximino-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on.Example 264 8- (4-Phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 8-(4-phenylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benz-oxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-10 ethylester.Prepared analogously to Example 6 from 8- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 103-104°C.Melting point: 103-104 ° C.
Udbytte: 60% af det teoretiske.Yield: 60% of theory.
Eksempel 265 8-[4-(3,4-Dimethoxy-phenylsulfoximino)-butoxy]-4,4-dime-15 thyl-4H-3,l-benzoxazin-2-on.Example 265 8- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 8-[4-(3,4-dimethoxy-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 8- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl hydroxamic acid ethyl ester.
20 Smeltepunkt: 120-121°C.Melting point: 120-121 ° C.
Udbytte: 74,3% af det teoretiske.Yield: 74.3% of theory.
Eksempel 266 8-[4-(4-Acetamido-pheny1sulfoximino)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 266 8- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 6 ud fra 8-[4-(4-acetamido-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 8- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid. ethyl ester.
Smeltepunkt: 166-167°C.Melting point: 166-167 ° C.
30 Udbytte: 56,6% af det teoretiske.Yield: 56.6% of theory.
Eksempel 267 6-[4-(3,4-Dimethyl-phenylsulfoximino)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 267 6- [4- (3,4-Dimethyl-phenylsulfoximino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 124Prepared analogously to Example 6 from 124
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6-[4-(3,4-dimethyl-phenylsulfinyl)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-hydroxamic acid ethyl ester.
Smeltepunkt: 104-105°C.Melting point: 104-105 ° C.
5 Udbytte: 52,7% af det teoretiske.Yield: 52.7% of theory.
Eksempel 268 6-[4-(3,4-Dimethoxy-phenylsulfoximino)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 268 6- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 10 6-[4-(3,4-dimethoxy-phenylsulfinyl)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.
Smeltepunkt: 93-95°C.Melting point: 93-95 ° C.
Udbytte: 36,9% af det teoretiske.Yield: 36.9% of theory.
15 Eksempel 269 6-[4-(4-Cyclohexyl-phenylsulfoximino)-butoxy]-4,4-di-ethyl-4H-3,l-benzoxazin-2-on.Example 269 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-cyclohexyl-phenylsulfinyl)-butoxy]-4,4-diethyl-20 4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid. ethyl ester.
Smeltepunkt: 158-160°C.Melting point: 158-160 ° C.
Udbytte: 36,6% af det teoretiske.Yield: 36.6% of theory.
Eksempel 270 25 6-[4-(4-AcetamidnoTphenylsulfoximino)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on.Example 270 6- [4- (4-Acetamide phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-acetamido-phenylsulfinyl)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-30 hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-hydroxamic acid ethyl ester.
Smeltepunkt: 144-146°C.Melting point: 144-146 ° C.
Udbytte: 64,0% af det teoretiske.Yield: 64.0% of theory.
UIV IOH-OOV DUIV IOH-OOV D
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Eksempel 271 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4, 4-diethyl-4H-3,l-benzoxazin-2-on.Example 271 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 5 6-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 5- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.
Smeltepunkt: 136-138°C.Melting point: 136-138 ° C.
Udbytte: 68,7% af det teoretiske.Yield: 68.7% of theory.
10 Eksempel 272 6-(4-Phenylsulfoximino-butoxy)-4,4-diethyl-4H-3,1-benzoxaz in-2-on.Example 272 6- (4-Phenylsulfoxymino-butoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-(4-phenylsulfinyl-butoxy)-4,4-diethyl-4H-3,1-benz-15 oxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- (4-phenylsulfinyl-butoxy) -4,4-diethyl-4H-3,1-benz-oxazin-2-one and O-mesitylenesulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 134-135°C.Melting point: 134-135 ° C.
Udbytte: 69,6% af det teoretiske.Yield: 69.6% of theory.
Eksempel 273 20 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4-methyl-4H-3,l-benzoxazin-2-on.Example 273 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4-methyl-4H- 3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-25 syre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 179-180°C.Melting point: 179-180 ° C.
Udbytte: 67,6% af det teoretiske.Yield: 67.6% of theory.
Eksempel 274 6-[4-(4-Methyl-phenylsulfoximino)-butoxy]-4-methyl-4H-30 3,l-benzoxazin-2-on.Example 274 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4-methyl-4H-3,1-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetydroxamic acid ethyl ester.
35 Smeltepunkt: 121-123°C.Melting point: 121-123 ° C.
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Udbytte: 45,5% af det teoretiske.Yield: 45.5% of theory.
Eksempel 275 6-[4-(4-Acetamido-phenylsulfoximino)-butoxy]-4-methyl-4H-3,l-benzoxazin-2-on.Example 275 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 6 ud fra 6- [4-(4-acetamido-phenylsulfinyl)-butoxy]-4-methyl-4H- 3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-yre-ethy1ester.5 Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
Smeltepunkt: 123-125°C.Melting point: 123-125 ° C.
10 Udbytte: 45,2% af det teoretiske.Yield: 45.2% of theory.
Eksempel 276 7- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 276 7- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 15 7-[4-(3,4-dimethyl-phenylsulfoximino)-butoxy]-4,4-di- methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 7- [4- (3,4-dimethyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
oisland
Smeltepunkt: 151-153 C.Melting point: 151-153 ° C.
Udbytte: 70,0% af det teoretiske.Yield: 70.0% of theory.
Eksempel 277 20 7- [4- (4-Acetamido-N-acetyl-phenylsulfoximino) -butoxy].Example 277 20 7- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy].
4.4- dimethyl-4H-3,l-benzoxazin-2-on.4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 7- [4-acetamido-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 7- [4-acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
25 Smeltepunkt: 136-138°C.Melting point: 136-138 ° C.
Udbytte: 38,8% af det teoretiske.Yield: 38.8% of theory.
Eksempel 278 7-[4-(4-Methyl-N-acetyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,1-benzoxaz in-2-on.Example 278 7- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
30 Fremstillet analogt med eksempel 143 ud fra 7-[4-(4-methyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 7- [4- (4-methyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 142-144°C.Melting point: 142-144 ° C.
Udbytte: 50,7% af det teoretiske.Yield: 50.7% of theory.
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Eksempel 279 7-[4-(4-Chlor-N-acetyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 279 7- [4- (4-Chloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 7-[4-(4-chlor-phenylsulfoximino)-butoxy]-4,4-dimethyl- 4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 7- [4- (4-chloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 127-129°C.Melting point: 127-129 ° C.
Udbytte: 85,0% af det teoretiske.Yield: 85.0% of theory.
Eksempel 280 10 7-[4-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl~4H-3,l-benzoxazin-2-on.Example 280 7- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 7-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 7- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Smeltepunkt: 130-132°C.Melting point: 130-132 ° C.
Udbytte: 95,6% af det teoretiske.Yield: 95.6% of theory.
Eksempel 281 7-[4-(N-Acetyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 281 7- [4- (N-Acetyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 143 ud fra 7-(4-phenylsulfoximino-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 7- (4-phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 123-125°C.Melting point: 123-125 ° C.
Udbytte: 84,3% af det teoretiske.Yield: 84.3% of theory.
25 Eksempel 282 7-[4-(3,4-Dimethoxy-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 282 7- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 7-[4-(3,4-dimethoxy-phenylsulfoximino)-butoxy]-4,4-30 dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid. Smeltepunkt: 202-204°C.Prepared analogously to Example 143 from 7- [4- (3,4-dimethoxy-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 202-204 ° C.
Udbytte: 82,5% af det teoretiske.Yield: 82.5% of theory.
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Eksempel 283 8-[4-(4-Cyclohexyl-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 283 8- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 8-[4-(4-cyclohexyl-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 8- [4- (4-cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 167-168°C.Melting point: 167-168 ° C.
Udbytte: 92,9% af det teoretiske.Yield: 92.9% of theory.
Eksempel 284 10 8-[4-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 284 8- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 8-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 8- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Smeltepunkt: 170-171°C.Melting point: 170-171 ° C.
Udbytte: 100% af det teoretiske.Yield: 100% of theory.
Eksempel 285 8-[4-(3,4-Dimethyl-N-acetyl-phenylsolfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 285 8- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 143 ud fra 8-[4-(3,4-dimethyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 8- [4- (3,4-dimethyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 145-146°C.Melting point: 145-146 ° C.
Udbytte: 93,9% af det teoretiske.Yield: 93.9% of theory.
25 Eksempel 286 8- [- (N-Acetyl-phenyl sul f oximino) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 286 8- [- (N-Acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 8-(4-phenylsulfoximino-butoxy)-4,4-dimethyl-4H-3,1-30 benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 8- (4-phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1 -30-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 113-114°C.Melting point: 113-114 ° C.
Udbytte: 75,6% af det teoretiske.Yield: 75.6% of theory.
UIV ΐο^οου d 129UIV ΐο ^ οου d 129
Eksempel 287 8-[4- (3,4-Dimethoxy-N-acetyl-phenyls ulfoximino)-butoxt]- 4.4- ^dimethyl-4H-3,l-benzoxazin-2-on.Example 287 8- [4- (3,4-Dimethoxy-N-acetyl-phenyls-ulfoximino) -butox] - 4.4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 8-[4- (3,4-dimethoxy-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 8- [4- (3,4-dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 137-138°C.Melting point: 137-138 ° C.
Udbytte: 90,2% af det teoretiske.Yield: 90.2% of theory.
Eksempel 288 10 8- [4- (4-Acetamido-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 288 8- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 8- [4- (4-acetamido-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 8- [4- (4-acetamido-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Smeltepunkt: 183-184°C.Melting point: 183-184 ° C.
Udbytte: 88,6% af det teoretiske.Yield: 88.6% of theory.
Eksempel 289 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- diethyl-4H-3,l-benzoxazin-2-on.Example 289 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-cyclohexyl-phenylsulfoximino)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 176-178°C.Melting point: 176-178 ° C.
Udbytte: 87,3% af det teoretiske.Yield: 87.3% of theory.
25 Eksempel 290 6-[4-(3,4-Dimethyl-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- diethyl-4H-3,l-benzoxazin-2-on.Example 290 6- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6- [4- (3,4-dimethyl-phenylsulfoximino)-butoxy]-4,4-30 diethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (3,4-dimethyl-phenylsulfoximino) -butoxy] -4,4-30-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Harpiks, RF-værdi: 0,52 (kiselgelplade: chloroform/etha-nol = 9:1).Resin, RF value: 0.52 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 87,7% af det teoretiske.Yield: 87.7% of theory.
C26H34N2°5S (486'64> 35 Beregnet: C 64,17 H 7,04 N 5,76 S 6,59C26H34N2 ° 5S (486'64> 35 Calculated: C 64.17 H 7.04 N 5.76 S 6.59
Fundet : 63,90 6,90 5,51 6,94 130Found: 63.90 6.90 5.51 6.94 130
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Eksempel 291 6- [4- (4-Acetamido-N-acetyl-phenyls.ulfoximino) -butoxy] - 4.4- diethyl-4H-3,l-benzoxazin-2-on.Example 291 6- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[4-(4-acetamido-pbenylsulfoximino)-butoxy]-4,4-di- ethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5 6- [4- (4-acetamido-pbenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 146-149°C.Melting point: 146-149 ° C.
Udbytte: 88,6% af det teoretiske.Yield: 88.6% of theory.
Eksempel 292 10 6-[4-(3,4-Dimethoxy-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- diethyl-4H-3,l-benzoxazin-2-on.Example 292 6- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(3,4-dimethoxy-phenylsulfoximino)-butoxy]-4,4-diethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (3,4-dimethoxy-phenylsulfoximino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Harpiks, RF-værdi: 0,5 (kiselgelplade: chloroform/etha-nol = 9:1).Resin, RF value: 0.5 (silica gel plate: chloroform / ethanol = 9: 1).
Udbytte: 87,2% af det teoretiske.Yield: 87.2% of theory.
C26H34N2°7S (518,64)C26H34N2 ° 7S (518.64)
Beregnet: C 60,21 H 6,61 N 5,40 6,18 20 Fundet : 59,95 6,58 5,19 6,31Calculated: C 60.21 H 6.61 N 5.40 6.18 Found: 59.95 6.58 5.19 6.31
Eksempel 293 6-[4-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-butoxy]- 4.4- die.thyl-4H-3, l-benzoxazin-2-on.Example 293 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoximino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 43 ud fra 25 6-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]-4,4-di- ethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 43 from 6- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 164-166°C.Melting point: 164-166 ° C.
Udbytte: 86,6% af det teoretiske.Yield: 86.6% of theory.
Eksempel 294 30 6-[4-(N-Acetyl-phenylsulfoximino)-butoxy]-4,4-diethyl- 4H-3,l-benzoxazin-2-on.Example 294 6- [4- (N-Acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-(4-phenylsulfoximino-butoxy-4,4-diethyl-4H-3,1-benz-oxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- (4-phenylsulfoxymino-butoxy-4,4-diethyl-4H-3,1-benz-oxazin-2-one and acetanhydride.
35 Smeltepunkt: 120-122°C.Melting point: 120-122 ° C.
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Udbytte: 89,4% af det teoretiske.Yield: 89.4% of theory.
Eksempel 295 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 295 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 4 ud fra 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylsulfoximino)-butylbromid-mesity-lensulfonyl (smeltepunkt: 170-173°C) .Prepared analogously to Example 4 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfoximino) -butyl bromide mesitylsulfonyl (m.p. 170-173 ° C).
Smeltepunkt: 164-166°C.Melting point: 164-166 ° C.
10 Udbytte: 35,4% af det teoretiske.Yield: 35.4% of theory.
Eksempel 296 6-[4-(3,4-Dichlor-N-acetul-phenylsulfoximino)-butoxy]- 4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 296 6- [4- (3,4-Dichloro-N-acetul-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 15 6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-N-acetyl-phenylsulfoximino)-butylbromid (smeltepunkt: 78-79°C).Prepared analogously to Example 4 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-N-acetyl-phenylsulfoximino) -butyl bromide (m.p. 78-79 ° C).
Smeltepunkt: 156-158°C.Melting point: 156-158 ° C.
Udbytte: 66,5% af det teoretiske.Yield: 66.5% of theory.
20 Eksempel 297 6-(4-Phenylsulfinyl-butoxy)-4H-3,l-benzoxazin-2-on.Example 297 6- (4-Phenylsulfinyl-butoxy) -4H-3,1-benzoxazin-2-one.
4,2 g (0,0133 mol) 2-amino-5-(4-phenylsulfinyl-butoxy) -benzylalkohol (fremstillet ud fra 2-nitro-5-(4-phenylsulfinyl-butoxy)-benzylalkohol ved katalytisk 25 hydrogenering) opløstes i 150 ml chloroform og tilsattes 6,5 g (0,05 mol) kaliumcarbonat. Til denne blanding dryppedes langsomt under omrøring 10 ml 20%'ig opløsning af phosgen i toluen. Efter 2 timers efteromrøring vaskedes opløsningen med vand, tørredes med natriumsul-20 fat, og opløsningsmidlet afdestilleredes i vakuum.4.2 g (0.0133 mole) of 2-amino-5- (4-phenylsulfinyl-butoxy) -benzyl alcohol (prepared from 2-nitro-5- (4-phenylsulfinyl-butoxy) -benzyl alcohol by catalytic hydrogenation) were dissolved. in 150 ml of chloroform and 6.5 g (0.05 mol) of potassium carbonate were added. To this mixture was slowly added, with stirring, 10 ml of 20% solution of phosgene in toluene. After 2 hours of stirring, the solution was washed with water, dried over sodium sulfate and the solvent was distilled off in vacuo.
Resten omkrystalliseredes i eddikesyreethylester/cyclo-hexan.The residue was recrystallized from acetic acid ethyl ester / cyclohexane.
Smeltepunkt: 115-116°C.Melting point: 115-116 ° C.
Udbytte: 2,1 g (45,8% af det teoretiske).Yield: 2.1 g (45.8% of theory).
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Eksempel 298 7-(4-Phenylsulfoximino-butoxy)-4,4-dimethyl-4H-3,1-benzoxaz in-2-on.Example 298 7- (4-Phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
1,56 g (2,78 mmol) kaliumhydroxid opløstes i 5 10 ml methanol og tilsattes under omrøring ved stue temperatur 0,8 g (1,86 mmol) 7-[4-(N-acetyl-phenyl-sulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on. Den fremkomne klare opløsning henstilledes natten over, tilførte derefter vand, sugede bundfaldet af, 10 vaskede dette med vand og diisopropylether og tørrede det ved 60°C.Potassium hydroxide (1.56 g) (2.78 mmol) was dissolved in methanol (10 ml) and stirred at room temperature with 0.8 g (1.86 mmol) of 7- [4- (N-acetyl-phenylsulfoximino) -butoxy ] -4,4-dimethyl-4H-3, l-benzoxazin-2-one. The resulting clear solution was left to stand overnight, then added to water, suction precipitated, washed with water and diisopropyl ether and dried at 60 ° C.
Smeltepunkt: 130-132°C.Melting point: 130-132 ° C.
Udbytte: 0,65 g (90% af det teoretiske).Yield: 0.65 g (90% of theory).
Eksempel 299 15 7,8-Dibrom-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4- dimethyl-4H-3,l-benzoxazin-2-on.Example 299 7,8-Dibromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 7,8-dibrom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(4-methyl-phenylmercapto)-butylchlorid.Prepared analogously to Example 4 from 7,8-dibromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.
20 Smeltepunkt: 114-115°C.Melting point: 114-115 ° C.
Udbytte: 45,4% af det teoretiske.Yield: 45.4% of theory.
Eksempel 300 6-(4-Phenylsulfinyl-butoxy)-4,4,7-trimethyl-4H-3,1-benzoxazin-2-on.Example 300 6- (4-Phenylsulfinyl-butoxy) -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 4 ud fra 6-hydroxy-4,4,7-trimethyl-4H-3,l-benzoxazin-2-on og 4-phenylsulfiny1-butylbromid.Prepared analogously to Example 4 from 6-hydroxy-4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.
Smeltepunkt: 124-125°C.Melting point: 124-125 ° C.
Udbytte: 51,6% af det teoretiske.Yield: 51.6% of theory.
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Eksempel 301 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy] -4,4,7-tri-methyl-4H-3,l-benzoxazin-2-on.Example 301 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5 6-hydroxy-4,4,7-trimethyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylsulfonyl)-butylbromid.Prepared analogously to Example 4 from 5 6-hydroxy-4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfonyl) -butyl bromide.
Smeltepunkt: 151-152°C.Melting point: 151-152 ° C.
Udbytte: 42,3% af det teoretiske.Yield: 42.3% of theory.
Eksempel 302 10 6-[4-(4-Methyl-phenylmercapto)-butoxy]-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on.Example 302 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og 4-methyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 4-methylthiophenol.
15 Smeltepunkt: 125-126°C.Melting point: 125-126 ° C.
Udbytte: 78,4% af det teoretiske.Yield: 78.4% of theory.
Eksempel 303 6-[4-(3,4-Dichlor-phenylmercapto)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on.Example 303 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4,8-trimethyl-4H-3,l-benzoxazin-2-og og 3,4-dichlor-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazine-2-and and 3,4-dichloro-thiophenol.
Smeltepunkt: 136-137°C.Melting point: 136-137 ° C.
Udbytte: 68,8% af det teoretiske.Yield: 68.8% of theory.
25 Eksempel 304 6-[4-(4-Acetamido-phenylmercapto)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on.Example 304 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4,8-trimethyl-4H-3,l-benzoxazin-2-30 on og 4-acetamido-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazine-2-30 one and 4-acetamido-thiophenol.
Smeltepunkt: 167-168°C.Melting point: 167-168 ° C.
Udbytte: 64,2% af det teoretiske.Yield: 64.2% of theory.
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Eksempel 305 6-[4-(2-Pyridylmercapto)-butoxy]-4,4,8-trimethyl-4H- 3,l-benzoxazin-2-on.Example 305 6- [4- (2-Pyridylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og 2-mercapto-pyridin.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 2-mercapto-pyridine.
Smelteounkt: 144-145°C.Melting point: 144-145 ° C.
Udbytte: 64,0% af det teoretiske.Yield: 64.0% of theory.
Eksempel 306 10 6-[4-(4-Chlor-phenylmercapto)-butoxy]-4,4,8-trimethyl- 4H-3,l-benzoxazin-2-on.Example 306 6- [4- (4-Chloro-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og 4-chlor-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 4-chloro-thiophenol.
15 Smeltepunkt: 141-142°C.Melting point: 141-142 ° C.
Udbytte: 63,5% af det teoretiske.Yield: 63.5% of theory.
Eksempel 307 6-(4-Phenylmercapto-butoxy)-4,4,8-trimethyl-4H-3,1-benzoxaz in-2-on.Example 307 6- (4-Phenylmercapto-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and thiophenol.
Smeltepunkt: 125-126°C.Melting point: 125-126 ° C.
Udbytte: 83,1% af det teoretiske.Yield: 83.1% of theory.
25 Eksempel 308 6-[4-(3,4-Dimethyl-phenylmercapto)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on.Example 308 6- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 6-(4-chlorbutoxy)-4,4,8-trimethyl-4H-3,l-benzoxazin-30 2-on og 3,4-dimethyl-thiophenol.Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethyl-thiophenol.
Smeltepunkt: 146-147°C.Melting point: 146-147 ° C.
Udbytte: 78,1% af det teoretiske.Yield: 78.1% of theory.
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Eksempel 309 6-[4-(3,4-Dimethoxy-phenylmercapto)-butoxy]-4,4,8-tri-methyl-4H~3,l-benzoxazin-2-on.Example 309 6- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-1,3-benzoxazin-2-one.
Fremstillet analogt med eksempel 1 ud fra 5 6-(4-chlorbutoxy)-4,4,8-trimethyl-4H-3,1-benzoxazin- 2-on og 3,4-dimethoxy-thiophenol.Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.
Smeltepunkt: 130-131°C.Melting point: 130-131 ° C.
Udbytte: 73,3% af det teoretiske.Yield: 73.3% of theory.
Eksempel 310 10 6-[4-(4-Acetamido-phenylsulfinyl)-butoxy]-7-nitro-4,4- dimethyl-4H-3,l-benzoxazin-2-on.Example 310 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-acetamido-phenylmercapto)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 240-241°C.Melting point: 240-241 ° C.
Udbytte: 72,6% af det teoretiske.Yield: 72.6% of theory.
Eksempel 311 6-[4-(4-Chlor-phenylsulfinyl)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 311 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-chlor-phenylmercapto)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 159-160°C.Prepared analogously to Example 2 from 6- [4- (4-chloro-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 159-160 ° C.
Udbytte: 83,4% af det teoretiske.Yield: 83.4% of theory.
25 Eksempel 312 6-[4-(2-Pyridylsulfinyl)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 312 6- [4- (2-Pyridylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(2-pyridylmercapto)-butoxy]-7-nitro-4,4-dimethyl-30 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (2-pyridylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 156-157°C.Melting point: 156-157 ° C.
Udbytte: 69,1% af det teoretiske.Yield: 69.1% of theory.
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Eksempel 313 6-[4-(4-Methyl-phenylsulfinyl)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 313 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-[4-(4-methyl-phenylmercapto)-butoxy]-7-nitro-4,4 - dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 176-177°C.Prepared analogously to Example 2 from 5 6- [4- (4-methyl-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 176-177 ° C.
Udbytte: 76,1% af det teoretiske.Yield: 76.1% of theory.
Eksempel 314 10 6-[4- (3,4-Dimethoxy-phenylsulfinyl)-butoxy]-7-nitro- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 314 6- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4- (3,4-dimethoxy-phenylmercapto)-butoxy]-7-nitro- 4.4- dimethyl-3H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-3H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 190-192°C.Melting point: 190-192 ° C.
Udbytte: 84,3% af det teoretiske.Yield: 84.3% of theory.
Eksempel 315 6-[4-(3,4-Dimethyl-phenylsulfinyl)-butoxy]-7-nitro- 4.4- dimethyl-4H-3,l-benzoxazin-2-on.Example 315 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4- (3,4-dimethyl-phenylmercapto)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 146-147°C.Prepared analogously to Example 2 from 6- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 146-147 ° C.
Udbytte: 68,2% af det teoretiske.Yield: 68.2% of theory.
25 Eksempel 316 8-Chlor-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 316 8-Chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 8-chlor-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-30 dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 113-114°C.Prepared analogously to Example 2 from 8-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 113-114 ° C.
Udbytte: 90,3% af det teoretiske.Yield: 90.3% of theory.
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Eksempel 317 7- Chlor-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 317 7- Chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 7-chlor-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 143-144°C.Prepared analogously to Example 2 from 5 7-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 143-144 ° C.
Udbytte: 85,3% af det teoretiske.Yield: 85.3% of theory.
Eksempel 318 10 6- [4-(4-Chlor-phenylsulfinyl)-butoxy]-8-chlor-4,4-di- methyl-4H-3,l-benzoxazin-2-οη.Example 318 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -8-chloro-4,4-dimethyl-4H-3,1-benzoxazine-2-oη.
Fremstillet analogt med eksempel 2 ud fra 8- chlor-6-[4-(4-chlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 8- chloro-6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 83-85°C.Melting point: 83-85 ° C.
Udbytte: 78,1% af det teoretiske.Yield: 78.1% of theory.
Eksempel 319 6- [4-(4-Chlor-phenylsulfinyl)-butoxy]-7-chlor-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 319 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -7-chloro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 7- chlor-6-[4-(4-chlor-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 162-163°C.Prepared analogously to Example 2 from 7- chloro-6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 162-163 ° C.
Udbytte: 86% af det teoretiske.Yield: 86% of theory.
25 Eksempel 320 7-Brom-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-di-methyl-4H-3,l-benzoxazin-2-on.Example 320 7-Bromo-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 7-brom-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-30 dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 143-145°C.Prepared analogously to Example 2 from 7-bromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 143-145 ° C.
Udbytte: 78,5% af det teoretiske.Yield: 78.5% of theory.
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Eksempel 321 8-Brom-6-[4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 321 8-Bromo-6- [4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 8-brom-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4- dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 123-124°C.Prepared analogously to Example 2 from 5 8-bromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 123-124 ° C.
Udbytte: 86,4% af det teoretiske.Yield: 86.4% of theory.
Eksempel 322 10 6-[4-(4-Methyl-phenylsulfinyl)-butoxy]-4,4,7-trimethyl- 4H-3,l-benzoxazin-2-on.Example 322 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4,7-trimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 152-153°C.Melting point: 152-153 ° C.
Udbytte: 87,2% af det teoretiske.Yield: 87.2% of theory.
Eksempel 323 7.8- Dibrom-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 323 7.8- Dibromo-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 7.8- dibrom-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 138-139°C.Prepared analogously to Example 2 from 7,8-dibromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 138-139 ° C.
Udbytte: 70,0% af det teoretiske.Yield: 70.0% of theory.
25 Eksempel 324 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on.Example 324 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dichlor-phenylmercapto)-butoxy]-4,4,8-tri-30 methyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 158°C.Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 158 ° C.
Udbytte: 68% af det teoretiske.Yield: 68% of theory.
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Eksempel 325 6-[4-(4-Methyl-phenylsulfinyl)-butoxyj-4,4,8-trimethyl-4H-3,l-benzoxazin~2-on.Example 325 6- [4- (4-Methyl-phenylsulfinyl) -butoxy-4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4,8-trimethyl- 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 137-138°C.Melting point: 137-138 ° C.
Udbytte: 40% af det teoretiske.Yield: 40% of theory.
Eksempel 326 10 6-[4-(4-Chlor-phenylsulfinyl)-butoxy]-4,4,8-trimethyl- 4H-3,l-benzoxazin-2-on.Example 326 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-chlor-phenylmercapto)-butoxy]-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 163-164°C.Melting point: 163-164 ° C.
Udbytte: 66,2% af det teoretiske.Yield: 66.2% of theory.
Eksempel 327 6-[4-(3,4-Dimethoxy-phenylsulfinyl)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on.Example 327 6- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dimethoxy-phenylmercapto)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 142-143°C.Prepared analogously to Example 2 from 6- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 142-143 ° C.
Udbytte: 70,5% af det teoretiske.Yield: 70.5% of theory.
25 Eksempel 328 6-[4-(3,4-Dimethyl-phenylsulfinyl)-butoxy]-4,4,8-trime thyl-4H- 3 ,l-benzoxazin-2-on.Example 328 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(3,4-dimethyl-phenylmercapto)-butoxy]-4,4,8-tri-30 methyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 113-114°C.Prepared analogously to Example 2 from 6- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 113-114 ° C.
Udbytte: 72,9% af det teoretiske.Yield: 72.9% of theory.
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Eksempel 329 6-(4-Phenylsulfinyl-butoxy)-4,4,8-trimethyl-4H-3,1-benzoxazin-2-on.Example 329 6- (4-Phenylsulfinyl-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 6-(4-phenylmercapto-butoxy)-4,4,8-trimethyl-4H-3,1- benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 6- (4-phenylmercapto-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 143-144°C.Melting point: 143-144 ° C.
Udbytte: 77,6% af det teoretiske.Yield: 77.6% of theory.
Eksempel 330 10 6-[4-(4-Acetamido-phenylsulfinyl)-butoxy]-4,4,8-trime- thyl-4H-3,l-benzoxazin-2-on.Example 330 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-acetamido-phenylmercapto)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 212-213°C.Melting point: 212-213 ° C.
Udbytte: 57,9% af det teoretiske.Yield: 57.9% of theory.
Eksempel 331 6-[4-(2-Pyridylsulfinyl)-butoxy]-4,4,8-trimethyl-4H- 3.1- benzoxazin-2-on.Example 331 6- [4- (2-Pyridylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3.1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4-(2-pyridylmercapto)-butoxy]-4,4,8-trimethyl-4H- 3.1- benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (2-pyridylmercapto) butoxy] -4,4,8-trimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 163-164°C.Melting point: 163-164 ° C.
Udbytte: 65,8% af det teoretiske.Yield: 65.8% of theory.
25 Eksempel 332 6-[4-(3,4-Dimethoxy-phenylsulfoximino)-butoxy]-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on.Example 332 6- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dimethoxy-phenylsulfinyl)-butoxy]-4,4,8-tri-30 methyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one and O- mesitylenesulfonyl-acethydroxamsyre acid ethyl ester.
Smeltepunkt: 175-176°C.Melting point: 175-176 ° C.
Udbytte: 58,7% af det teoretiske.Yield: 58.7% of theory.
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Eksempel 333 6-[4-(3,4-Dimethyl-phenylsulfoximino)-butoxy]-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on.Example 333 6- [4- (3,4-Dimethyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 5 6-[4-(3,4-dimethyl-phenylsulf inyl)-butoxy]-4,4,8-tri- methyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 5- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 0 -mesitylensulfonyl-acethydroxamsyre acid ethyl ester.
Smeltepunkt: 174-175°C.Melting point: 174-175 ° C.
Udbytte: 61,8% af det teoretiske.Yield: 61.8% of theory.
10 Eksempel 334 6-(4-Phenylsulfoximino-butoxy)-4,4,8-trimethyl-4H-3,1-benzoxazin-2-on.Example 334 6- (4-Phenylsulfoxymino-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-(4-phenylsulfinyl-butoxy)-4,4,8-trimethyl-4H-3,1-15 benzoxazin-2-on og O-mesitylensulfonyl-acethydrazamsy-re-ethylester.Prepared analogously to Example 6 from 6- (4-phenylsulfinyl-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydrazamic acid ethyl ester.
Smeltepunkt: 147-148°C.Melting point: 147-148 ° C.
Udbytte: 66,8% af det teoretiske.Yield: 66.8% of theory.
Eksempel 335 20 6-[4- (3,4-Dichlor-phenylsulfoximino)-butoxy]-4,4,8- trimethyl-4H-3,l-benzoxazin-2-on.Example 335 6- [4- (3,4-Dichloro-phenylsulfoximino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dichlor-phenylsulfinyl) -butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-25 acethydroxamzyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl -25 acetyl hydroxamic acid ethyl ester.
Smeltepunkt: 116-117°C.Melting point: 116-117 ° C.
Udbytte: 50,0% af det teoretiske.Yield: 50.0% of theory.
Eksempel 336 6- [ 4- (4-Chlor-phenylsulf oximino) -butoxy] -4,4,8-tri-30 methyl-4H-3,l-benzoxazin-2-on.Example 336 6- [4- (4-Chloro-phenylsulfoxymino) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-chlor-phenylsulfinyl)-butoxy]-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl hydroxamic acid ethyl ester.
35 Smeltepunkt: 167-168°C.Melting point: 167-168 ° C.
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Udbytte: 72,8% af det teoretiske.Yield: 72.8% of theory.
Eksempel 337 6-[4-(4-Methyl-phenylsulfoximino)-butoxy]-4,4,8-trime-thyl-4H-3,l-benzoxazin-2-on.Example 337 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-methyl-phenylsulfinyl)-butoxy)-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.
Smeltepunkt: 183-184°C.Melting point: 183-184 ° C.
10 Udbytte: 71,5% af det teoretiske.Yield: 71.5% of theory.
Eksempel 338 6-[4-Acetamido-phenylsulfoximino)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on.Example 338 6- [4-Acetamido-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 15 6-[4-(4-acetamido-phenylsulfinyl)-butoxy]-4,4,8-tri- methyl-4H-3,l-benzoxazon-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazone-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.
Smeltepunkt: 168-169°C.Melting point: 168-169 ° C.
Udbytte: 66,1% af det teoretiske.Yield: 66.1% of theory.
20 Eksempel 339 6-[4-(4-Acetamido-phenylsulfoximino)-butoxy]-4,4-dime-thyl-7-nitro-4H-3,l-benzoxazin-2-on.Example 339 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6- [4-(4-acetamido-phenylsulfinyl)-butoxy]-4,4-dimethyl-25 7-nitro-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl- acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.
Smeltepunkt: 209-211°C.Melting point: 209-211 ° C.
Udbytte: 55,4% af det teoretiske.Yield: 55.4% of theory.
Eksempel 340 30 6-[4-(4-Chlor-phenylsulfoximino)-butoxy]-4,4-dimethyl- 7- nitro-4H-3,l-benzoxazin-2-on.Example 340 6- [4- (4-Chloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-chlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-7-nitro-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl- 143 acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-143 acethydroxamsyre acid ethyl ester.
Smeltepunkt: 116-118°C.Melting point: 116-118 ° C.
Udbytte: 88,3% af det teoretiske.Yield: 88.3% of theory.
Eksempel 341 5 6-[4-(4-Methyl-phenylsulfoximino)-butoxy]-4,4-dimethyl- 7-nitro-4H-3,l-benzoxazin-2-on.Example 341 6- [4- (4-Methyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-7-nitro-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-10 acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-10 acethydroxamsyre acid ethyl ester.
Smeltepunkt: 112-114°C.Melting point: 112-114 ° C.
Udbytte: 86,2% af det teoretiske.Yield: 86.2% of theory.
Eksempel 342 6-[4-(3,4-Dimethoxy-phenylsulfoximino)-butoxy]-4,4-15 dimethyl-7-nitro-4H-3,l-benzoxazin-2-on.Example 342 6- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dimethoxy-phenylsulfinyl)-butoxy]-4,4-dime-thyl-7-nitro-4H-3,l-benzoxazin-2-on og O-mesitylensul-fony1-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and 0 -mesitylensul-fony1-acethydroxamsyre acid ethyl ester.
20 Smeltepunkt: 147-149°C.Melting point: 147-149 ° C.
Udbytte: 41,4% af det teoretiske.Yield: 41.4% of theory.
Eksempel 343 6-[4-(3,4-Dimethyl-phenylsulfoximino)-butoxy]-4,4-di-methyl-7-nitro-4H-3,l-benzoxazin-2-on.Example 343 6- [4- (3,4-Dimethyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.
25 Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dimethyl-phenylsulfinyl)-butoxy]-4-4-dime-thyl-7-nitro-4H-3,l-benzoxazin-2-on og O-mesitylensul-fonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4-4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and mesitylensul-O-sulfonyl-acethydroxamsyre acid ethyl ester.
Smeltepunkt: 145-146°C.Melting point: 145-146 ° C.
30 Udbytte: 67% af det teoretiske.Yield: 67% of theory.
Eksempel 344 8-Chlor-6-[4-(3,4-dichlor-phenylsukfoximino)-butoxy]- 4,4-dimethyl-4H~3,l-benzoxazin-2-on.Example 344 8-Chloro-6- [4- (3,4-dichloro-phenylsuccoximino) -butoxy] -4,4-dimethyl-4H-1,3-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 144Prepared analogously to Example 6 from 144
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8-chlor-6-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfo-nul-acethydroxamsyre-ethylester.8-Chloro-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonylacethydroxamic acid ethyl ester.
Smeltepunkt: 135-136°C.Melting point: 135-136 ° C.
5 Udbytte: 74,3% af det teoretiske.Yield: 74.3% of theory.
Eksempel 345 7- Chlor-6-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]- 4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 345 7- Chloro-6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 10 7-chlor-6-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 7-Chloro-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O- mesitylenesulfonyl-acethydroxamsyre acid ethyl ester.
Smeltepunkt: ved 87°C.Melting point: at 87 ° C.
Udbytte: 58,3% af det teoretiske.Yield: 58.3% of theory.
15 Eksempel 346 8- Chlor-6-[4-(4-methyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 346 8- Chloro-6- [4- (4-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 8-chlor-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-20 dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylénsulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 8-chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.
Smeltepunkt: 132-133°C.Melting point: 132-133 ° C.
Udbytte: 55,1% af det teoretiske.Yield: 55.1% of theory.
Eksempel 347 25 7-Chlor-6-[4-(4-methyl-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 347 7-Chloro-6- [4- (4-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 7-chlor-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-3 0 acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 7-chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-3 0 acetyl hydroxamic acid ethyl ester.
Smeltepunkt: 115-116°C.Melting point: 115-116 ° C.
Udbytte: 55,1% af det teoretiske.Yield: 55.1% of theory.
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Eksempel 348 8-Chlor-6-[4-(4-chlor-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 348 8-Chloro-6- [4- (4-chloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 5 8-chlor-6-[4-(4-chlor-phenylsulfonyl)-butoxy]-4,4- dimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 5 8-chloro-6- [4- (4-chloro-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.
Smeltepunkt: 162-163°C.Melting point: 162-163 ° C.
Udbytte: 57% af det teoretiske.Yield: 57% of theory.
10 Eksempel 349 7-Chlor-6-[4-(4-chlor-phenylsulfoximino)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 349 7-Chloro-6- [4- (4-chloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 7-chlor-6-[4-(4-chlor-phenylsulfinyl)-butoxy]-4,4-dime-15 thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxamsyre-ethylester.Prepared analogously to Example 6 from 7-chloro-6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O- mesitylenesulfonyl-acethydroxamsyre acid ethyl ester.
Smeltepunkt: 132-133°C.Melting point: 132-133 ° C.
Udbytte: 65,8% af det teoretiske.Yield: 65.8% of theory.
Eksempel 350 20 6-[4-(3,4-Dichlor-phenylsulfoximino)-butoxy]-4,4,7- trimethyl-4K-3,l-benzoxazin-2-on.Example 350 6- [4- (3,4-Dichloro-phenylsulfoximino) -butoxy] -4,4,7-trimethyl-4K-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4,4,7-trime-thyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-25 hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl -acet-hydroxamic acid ethyl ester.
Smeltepunkt: 135-137°C.Melting point: 135-137 ° C.
Udbytte: 63,6% af det teoretiske.Yield: 63.6% of theory.
Eksempel 351 6-(4-Phenylsulfoximino-butoxy)-4,4,7-trimethyl-4H-3,1-30 benzoxazin-2-on.Example 351 6- (4-Phenylsulfoxymino-butoxy) -4,4,7-trimethyl-4H-3,1-30-benzoxazin-2-one.
Fremstillet analogt med eksempel 6 ud fra 6-(4-phenylsulfinyl-butoxy)-4,4,7-trimethyl-4H-3,1-benzoxazin-2-on og O-mesitylensulfonyl-acethydroxam-syre-ethylester.Prepared analogously to Example 6 from 6- (4-phenylsulfinyl-butoxy) -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.
35 Smeltepunkt: 123-124°C.Melting point: 123-124 ° C.
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Udbytte: 77% af det teoretiske.Yield: 77% of theory.
Eksempel 352 6-[4-(4-Methyl-phenylsulfoximino)-butoxy]-4,4,7-trime-thyl-4H-3,l-benzoxazin-2-on.Example 352 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.
5 Fremstillet analogt med eksempel 6 ud fra 6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4,7-trimethyl-4H-3,l-benzoxazin-2-on og O-mesitylensulfonyl-acet-hydroxamsyre-ethylester.Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.
Smeltepunkt: 153-154°C.Melting point: 153-154 ° C.
10 Udbytte: 57,6% af det teoretiske.Yield: 57.6% of theory.
Eksempel 353 6- [-(4-Acetamido-N-acetyl-phenylsulfoximino)-butoxy]- 7- nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 353 6- [- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 15 6-[4-(4-acetamido-phenylsulfoximino)-butoxy]-7-nitro- 4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid. Smeltepunkt: 250-252°C.Prepared analogously to Example 143 from 6- [4- (4-acetamido-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 250-252 ° C.
Udbytte: 92% af det teoretiske.Yield: 92% of theory.
Eksempel 354 20 6-[4-(4-Chlor-N-acetyl-phenylsulfoximino)-butoxy]-7- nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 354 6- [4- (4-Chloro-N-acetyl-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-chlor-phenylsulfoximino)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-chloro-phenylsulfoximino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
25 Smeltepunkt: 211-213°C.Melting point: 211-213 ° C.
Udbytte: 82,4% af det teoretiske.Yield: 82.4% of theory.
Eksempel 355 6-[4-(4-Methyl-N-acetyl-phenylsulfoximino)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 355 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
30 Fremstillet analogt med eksempel 143 ud fra 6-[4-(4-methyl-phenylsulfoximino)-butoxy]-7-nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 214-216°C.Melting point: 214-216 ° C.
Udbytte: 85,8% af det teoretiske.Yield: 85.8% of theory.
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Eksempel 356 6- [4-(3,4-Dimethoxy-N-acetyl-phenylsulfoximino)-butoxy]- 7- nitro-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 356 6- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[4-(3,4-dimethoxy-phenylsulfoximino)-butoxy]-7-nitro- 4,4-dimethyl-4H-3fl-benzoxazin-2-on og acetanhydrid. Smeltepunkt: 120-122°C.Prepared analogously to Example 143 from 5 6- [4- (3,4-dimethoxy-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3fl-benzoxazin-2-one and acetanhydride. Melting point: 120-122 ° C.
Udbytte: 82,2% af det teoretiske.Yield: 82.2% of theory.
Eksempel 357 10 6-[4-(3,4-Dimethoxy-N-acetyl-phenylsulfoximino)-butoxy]- 4.4.8- trimethyl-4H-3,l-benzoxazin-2-on.Example 357 6- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6-[4-(3,4-dimethoxy-phenylsulfoximino)-butoxy]-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (3,4-dimethoxy-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Smeltepunkt: 123-124°C.Melting point: 123-124 ° C.
Udbytte: 76,5% af det teoretiske.Yield: 76.5% of theory.
Eksempel 358 6-[4-(3,4-Dimethyl-N-acetyl-phenylsulfoximino)-butoxy]- 4.4.8- trimethyl-4H-3,l-benzoxazin-2-on.Example 358 6- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 143 ud fra 6-[4-(3,4-dimethyl-phenylsulfoximino)-butoxy]-4,4,8-trimethyl-4H-3,l-benzoxazin-2-on og acetanhydrid. Smeltepunkt: 146-147°C.Prepared analogously to Example 143 from 6- [4- (3,4-dimethyl-phenylsulfoximino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 146-147 ° C.
Udbytte: 83,1% af det teoretiske.Yield: 83.1% of theory.
25 Eksempel 359 6-[4-(N-Acetyl-phenylsulfoximino)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on.Example 359 6- [4- (N-Acetyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 43 ud fra 6-(4-phenylsulfoximino-butoxy)-4,4,8-trimethyl-4H-3,1-30 benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 43 from 6- (4-phenylsulfoxymino-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt: 99-100°C.Melting point: 99-100 ° C.
Udbytte: 71,0% af det teoretiske.Yield: 71.0% of theory.
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Eksempel 360 6-[4-(3,4-Dichlor-N-acetyl-phenylsulfoximino)-butoxy]- 4,4,8-trimethyl-4H-3,l-benzoxazin-2-on.Example 360 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoximino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 5 6-[4-(3,4-dichlor-phenylsulfoximino)-butoxy]-4,4,8-tri- methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 5- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
Smeltepunkt; 140-141°C.Melting point; 140-141 ° C.
Udbytte; 76,9% af det teoretiske.Yield; 76.9% of theory.
Eksempel 361 10 6-[4-(4-Chlor-N-acetyl-phenylsulfoximino)-butoxy]-4,4,8- trimethyl-4H-3,l-benzoxazin-2-on.Example 361 6- [4- (4-Chloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 143 ud fra 6- [4-(4-chlor-phenylsulfoximino)-butoxy]-4,4,8-tri-methyl-4H-3,l-benzoxazin-2-on og acetanhydrid.Prepared analogously to Example 143 from 6- [4- (4-chloro-phenylsulfoximino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.
15 Smeltepunkt: 178-179°C.Melting point: 178-179 ° C.
Udbytte; 79,9% af det teoretiske.Yield; 79.9% of theory.
Eksempel 362 8-Chlor-6-[4- (3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 362 8-Chloro-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 4 ud fra 8-chlor-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylsulfinyl)-butylbromid.Prepared analogously to Example 4 from 8-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.
Smeltepunkt: 121-122°C.Melting point: 121-122 ° C.
Udbytte: 62,0% af det teoretiske.Yield: 62.0% of theory.
25 Eksempel 363 7- Chlor-6-[4- (3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 363 7- Chloro-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 7-chlor-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 4-(3,4-dichlor-phenylsulfinyl)-butylbromid.Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.
Smeltepunkt: 125-127°C.Melting point: 125-127 ° C.
Udbytte: 41,5% af det teoretiske.Yield: 41.5% of theory.
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Eksempel 364 8-Chlor-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 364 8-Chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5 8-chlor-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(4-methyl-phenylmercapto)-butylchlorid. Smeltepunkt; 111-112°C.Prepared analogously to Example 4 from 5 8-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride. Melting point; 111-112 ° C.
Udbytte; 56,0% af det teoretiske.Yield; 56.0% of theory.
Eksempel 365 10 8-Chlor-6-(4-phenylsulfinyl-butoxy)-4,4-dimethyl-4H- 3.1- benzoxaz in-2-on.Example 365 8-Chloro-6- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 8-chlor-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-phenylsulfinyl-butylbromid.Prepared analogously to Example 4 from 8-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.
15 Smeltepunkt; 154-155°C.Melting point; 154-155 ° C.
Udbytte; 39,3% af det teoretiske.Yield; 39.3% of theory.
Eksempel 366 7-Chlor-6- (4-phenylsulfonyl-butoxy) -4,4-dimethyl-4H- 3.1- benzoxazin-2-on.Example 366 7-Chloro-6- (4-phenylsulfonyl-butoxy) -4,4-dimethyl-4H-3.1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 4 ud fra 7-chlor-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-phenylsulfinyl-butylbromid.Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.
Smeltepunkt; 124-125°C.Melting point; 124-125 ° C.
Udbytte: 31,5% af det teoretiske.Yield: 31.5% of theory.
25 Eksempel 367 7-Chlor-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 367 7-Chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 7-chlor-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 4-(4-methyl-phenylmercapto)-butylchlorid. Smeltepunkt: 118-119°C.Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4- (4-methyl-phenylmercapto) -butyl chloride. Melting point: 118-119 ° C.
Udbytte: 52,6% af det teoretiske.Yield: 52.6% of theory.
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Eksempel 368 7-Brom-6-[4-(3,4-dichlor-phenylsulfonyl)-butoxy]-4,4-dimethy1-4H-3,1-benzoxaz in-2-on.Example 368 7-Bromo-6- [4- (3,4-dichloro-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5 7-brom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(3,4-dichlor-phenylsulfinyl)-butylbromid.Prepared analogously to Example 4 from 5 7-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.
Smeltepunkt: 136-138°C.Melting point: 136-138 ° C.
Udbytte: 75,0% af det teoretiske.Yield: 75.0% of theory.
Eksempel 369 10 7-Brom-6-(4-phenylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1- benzoxazin-2-on.Example 369 10 7-Bromo-6- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 7- brom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-phenylsulfinyl-butylbromid.Prepared analogously to Example 4 from 7- bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.
15 Smeltepunkt: 119-120°C.Melting point: 119-120 ° C.
Udbytte: 53,1% af det teoretiske.Yield: 53.1% of theory.
Eksempel 370 8- Chlor-6-[4-(4-chlor-phenylmercapto)-butoxy]-4,4-dime-thyl-4H-3,1-benzoxazin-2-on.Example 370 8- Chloro-6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 4 ud fra 8-chlor-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(4-chlor-phenylmercapto)-butylchlorid.Prepared analogously to Example 4 from 8-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-chloro-phenylmercapto) -butyl chloride.
Smeltepunkt: 138-139°C.Melting point: 138-139 ° C.
Udbytte: 56,7% af det teoretiske.Yield: 56.7% of theory.
25 Eksempel 371 8-Brom-6-[4-(3,4-dichlor-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,1-benzoxazin-2-on..Example 371 8-Bromo-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 8-brom-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-on 30 og 4-(3,4-dichlor-phenylsulfinyl)-butylbromid.Prepared analogously to Example 4 from 8-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.
Smeltepunkt: 74°C.Melting point: 74 ° C.
Udbytte: 82,5% af det teoretiske.Yield: 82.5% of theory.
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Eksempel 372 8-Brom-6- (4-phenylsulfinyl-butoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-on.Example 372 8-Bromo-6- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5 8-brom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-phenylsulfinyl-butylbromid.Prepared analogously to Example 4 from 5 8-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.
Smeltepunkt: 129-130°C.Melting point: 129-130 ° C.
Udbytte: 41,1% af det teoretiske.Yield: 41.1% of theory.
Eksempel 373 10 7-Chlor-6-[4-(4-chlor-phenylmercapto)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 373 10 7-Chloro-6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 7-chlor-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(4-chlor-phenylmercapto)-butylchlorid.Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-chloro-phenylmercapto) -butyl chloride.
15 Smeltepunkt: 125-126°C.Melting point: 125-126 ° C.
Udbytte: 45,2% af det teoretiske.Yield: 45.2% of theory.
Eksempel 374 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,l-benzoxazin-2-on.Example 374 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 4 ud fra 6- hydroxy-4,4,7-trimethyl-4H-3,l-benzoxazin-2-on og 4-(4-methyl-phenylmercapto)-butylchlorid.Prepared analogously to Example 4 from 6- hydroxy-4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.
Smeltepunkt: 114-115°C.Melting point: 114-115 ° C.
Udbytte: 51,9% af det teoretiske.Yield: 51.9% of theory.
25 Eksempel 375 7- Brom-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 375 7- Bromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 7-brom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on 30 og 4-(4-methyl-phenylmercapto)-butylchlorid.Prepared analogously to Example 4 from 7-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4- (4-methyl-phenylmercapto) -butyl chloride.
Smeltepunkt: 122-123°C.Melting point: 122-123 ° C.
Udbytte: 43,3% af det teoretiske.Yield: 43.3% of theory.
DK 164860 BDK 164860 B
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Eksempel 376 8-Brom-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-dime-thyl-4H-3,l-benzoxazin-2-on.Example 376 8-Bromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5 8-brom-6-hydroxy-4,4-dimethyl-4H-3,l-benzoxazin-2-on og 4-(4-methyl-phenylmercapto)-butylchlorid.Prepared analogously to Example 4 from 5 8-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.
Smeltepunkt: 115-116°C.Melting point: 115-116 ° C.
Udbytte: 43,3% af det teoretiske.Yield: 43.3% of theory.
Eksempel 377 10 8-Chlor-6-[4-(4-methy1-phenylsulfinyl)-butoxy]-4H-3 ,1-benzoxazin-2-on.Example 377 10 8-Chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 8-chlor-6-[4-(4-methyl-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 8-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 114-115°C.Melting point: 114-115 ° C.
Udbytte: 72,7% af det teoretiske.Yield: 72.7% of theory.
Eksempel 378 6-[4-(4-Acetamido-phenylsulfinyl)-butoxy]-4,4,7-trime-thyl-4H-3,l-benzoxazin-2-on.Example 378 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6- [4 - (4-acetamido-phenylmercapto) -butoxy] - 4,4,7-trime-thyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 210-211°C.Melting point: 210-211 ° C.
Udbytte: 70,6% af det teoretiske.Yield: 70.6% of theory.
Eksempel 379 25 6-[4-(4-Methyl-phenylsulfinyl)-butoxy]-4,4,7-trime- thyl-4H-3,l-benzoxazin-2-on.Example 379 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4,7-trimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
30 Smeltepunkt: 152-153°C.Melting point: 152-153 ° C.
Udbytte: 87,2% af det teoretiske.Yield: 87.2% of theory.
UK I0400U DUK I0400U D
153153
Eksempel 380 8-Chlor-6-[4-(4-acetamido-phenylsulfinyl)-butoxy]-4H-3 ,l-benzoxazin-2-on.Example 380 8-Chloro-6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 8-chlor-6-[4-(4-acetamido-phenylmercapto)-butoxy]-4H-3 ,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 8-chloro-6- [4- (4-acetamido-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 130-132°C.Melting point: 130-132 ° C.
Udbytte: 85,0% af det teoretiske.Yield: 85.0% of theory.
Eksempel 381 10 5,7-Dimethyl-6-[4-(4-methyl-phenylmercapto)-butoxy]-4H- 3 ,l-benzoxazin-2-on.Example 381 10 5,7-Dimethyl-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5,7-dimethyl-6-hydroxy-4H-3,l-benzoxazin-2-on og 4-(4-methyl-phenylmercapto)-butylchlorid.Prepared analogously to Example 4 from 5,7-dimethyl-6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.
15 Smeltepunkt: 107-109°C.Melting point: 107-109 ° C.
Udbytte: 28,3% af det teoretiske.Yield: 28.3% of theory.
Eksempel 382 6-[4-(4-Methyl-phenylsulfinyl)-butoxy]-5,7-dimethyl-4H- 3.1- benzoxazin-2-on.Example 382 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -5,7-dimethyl-4H-3.1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 6-[4-(4-methyl-phenylmercapto)-butoxy]-5,7-dimethyl-4H- 3.1- benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -5,7-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 114-116°C.Melting point: 114-116 ° C.
Udbytte: 52,6% af det teoretiske.Yield: 52.6% of theory.
25 Eksempel 383 6-[4-(3,4-Dichlor-phenylsulfinyl)-butoxy]-5,7-dimethyl-4H-3,l-benzoxazin-2-on.Example 383 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -5,7-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 6-(4-(3,4-dichlor-phenylmercapto)-butoxy]-5,7-dimethyl-30 4H-3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 6- (4- (3,4-dichloro-phenylmercapto) -butoxy] -5,7-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 126-128°C.Melting point: 126-128 ° C.
Udbytte: 39,8% af det teoretiske.Yield: 39.8% of theory.
DK 164860 BDK 164860 B
154154
Eksempel 384 7-Chlor-6-[4-(4-methyl-phenylsufinyl)-butoxy]-4H-3,1-benzoxaz in-2-on.Example 384 7-Chloro-6- [4- (4-methyl-phenylsufinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5 7-chlor-6-[4-(4-methyl-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5 7-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 177-178°C.Melting point: 177-178 ° C.
Udbytte: 72,0% af det teoretiske.Yield: 72.0% of theory.
Eksempel 385 10 5-Chlor-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4H-3,1-benzoxaz in-2-on.Example 385 10 5-Chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5-chlor-6-[4-(4-methyl-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.
15 Smeltepunkt: 183-185°C.Melting point: 183-185 ° C.
Udbytte: 20,6% af det teoretiske.Yield: 20.6% of theory.
Eksempel 386 5.7- Dichlor-6-[4-(4-methyl-phenylsulfinyl)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 386 5.7- Dichloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 2 ud fra 5.7- dichlor-6-[4-(4-methyl-phenylmercapto)-butoxy]-4,4-dimethyl-4H-3,l-benzoxazin-2-on og hydrogenperoxid. Smeltepunkt: 169-170°C.Prepared analogously to Example 2 from 5.7-dichloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 169-170 ° C.
Udbytte: 75,0% af det teoretiske.Yield: 75.0% of theory.
25 Eksempel 387 5.7- Dichlor-6- (4-phenylsulf inyl-butoxy) -4,4-dimethyl-4H-3,l-benzoxazin-2-on.Example 387 5.7- Dichloro-6- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 2 ud fra 5.7- dichlor-6-(4-phenylmercapto-butoxy)-4,4-dimethyl-4H-30 3,l-benzoxazin-2-on og hydrogenperoxid.Prepared analogously to Example 2 from 5.7-dichloro-6- (4-phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.
Smeltepunkt: 186-187°C.Melting point: 186-187 ° C.
Udbytte: 74,0% af det teoretiske.Yield: 74.0% of theory.
155155
Eksempel 388 6- [4-(4-Acetamido-phenylmercapto)-butoxy]-4,4,7-trime-thyl-4H-3,l-benzoxazin-2-on.Example 388 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5 6-hydroxy-4,4,7-trimethyl-4H-3,l~benzoxazin-2-on og 4-(acetamido-phenylmercapto)-butylmesylat.Prepared analogously to Example 4 from 5 6-hydroxy-4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and 4- (acetamido-phenylmercapto) -butyl mesylate.
Smeltepunkt: 104-106°C.Melting point: 104-106 ° C.
Udbytte: 50,9% af det teoretiske.Yield: 50.9% of theory.
Eksempel 389 10 7-Chlor-6-[4-(4-methyl-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on.Example 389 10 7-Chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 7- chlor-6-hydroxy-4H~3,l-benzoxazin-2-on og 4-(4-methyl-phenylmercapto) -butylchlorid.Prepared analogously to Example 4 from 7- Chloro-6-hydroxy-4H ~ 3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.
15 Smeltepunkt: 145-147°C.Melting point: 145-147 ° C.
Udbytte: 44% af det teoretiske.Yield: 44% of theory.
Eksempel 390 7-CHlor-6-(4-phenylsulfinyl-butoxy)-4H-3,1-benzoxazin-2-on.Example 390 7-CHloro-6- (4-phenylsulfinyl-butoxy) -4H-3,1-benzoxazin-2-one.
20 Fremstillet analogt med eksempel 4 ud fra 7-chlor-6-hydroxy-4H-3,l-benzoxazin-2-on og 4-phenylsulf inyl-butylchlorid.Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl chloride.
Smeltepunkt: 177-179°C.Melting point: 177-179 ° C.
Udbytte: 18,1% af det teoretiske.Yield: 18.1% of theory.
25 Eksempel 391 5-Chlor-6-[4-(4-methyl-phenylmercapto)-butoxy]-4H-3,1-benzoxazin-2-on.Example 391 5-Chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.
Fremstillet analogt med eksempel 4 ud fra 5-chlor-6-hydroxy-4H-3,l-benzoxazin-2-on og 4-(4-methyl-3 0 phenylmercapto)-butylchlorid.Prepared analogously to Example 4 from 5-chloro-6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (4-methyl-30-phenylmercapto) -butyl chloride.
Smeltepunkt: 144-145°C.Melting point: 144-145 ° C.
Udbytte: 12,7% af det teoretiske.Yield: 12.7% of theory.
Claims (13)
Applications Claiming Priority (2)
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DE19823217012 DE3217012A1 (en) | 1982-05-06 | 1982-05-06 | BENZOXAZIN-2-ONE, THEIR PRODUCTION AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS |
DE3217012 | 1982-05-06 |
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DK195583D0 DK195583D0 (en) | 1983-05-03 |
DK195583A DK195583A (en) | 1983-11-07 |
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DK164860C DK164860C (en) | 1993-01-11 |
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US (1) | US4518597A (en) |
EP (1) | EP0093922B1 (en) |
JP (1) | JPS58203979A (en) |
KR (1) | KR900006546B1 (en) |
AT (1) | ATE24501T1 (en) |
AU (1) | AU563453B2 (en) |
CA (1) | CA1204744A (en) |
CS (1) | CS236876B2 (en) |
DD (1) | DD210453A5 (en) |
DE (2) | DE3217012A1 (en) |
DK (1) | DK164860C (en) |
ES (3) | ES8402585A1 (en) |
FI (1) | FI79704C (en) |
GB (1) | GB2119382B (en) |
GR (1) | GR79255B (en) |
HU (1) | HU194842B (en) |
IE (1) | IE55481B1 (en) |
IL (1) | IL68573A (en) |
NO (1) | NO158738C (en) |
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PL (1) | PL139119B1 (en) |
PT (1) | PT76627B (en) |
SU (1) | SU1138025A3 (en) |
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DE3439281A1 (en) * | 1984-10-26 | 1986-04-30 | Bayer Ag, 5090 Leverkusen | CHROMOGENIC 4,4-DIARYL-2-OXO-BENZO-3,1-OXAZINE, THEIR PRODUCTION AND USE |
US5519021A (en) * | 1992-08-07 | 1996-05-21 | Merck & Co., Inc. | Benzoxazinones as inhibitors of HIV reverse transcriptase |
IL106507A (en) * | 1992-08-07 | 1997-11-20 | Merck & Co Inc | Pharmaceutical compositions containing benzoxazinones and some novel compounds of this type |
US5874430A (en) * | 1996-10-02 | 1999-02-23 | Dupont Pharmaceuticals Company | 4,4-disubstitued-1,4-dihydro-2H-3,1-benzoxazin-2-ones useful as HIV reverse transcriptase inhibitors and intermediates and processes for making the same |
US5965729A (en) * | 1997-02-05 | 1999-10-12 | Merck & Co., Inc. | Process for the crystallization of a reverse transcriptase inhibitor using an anti-solvent |
US6509334B1 (en) | 1999-05-04 | 2003-01-21 | American Home Products Corporation | Cyclocarbamate derivatives as progesterone receptor modulators |
UA73119C2 (en) * | 2000-04-19 | 2005-06-15 | American Home Products Corpoir | Derivatives of cyclic thiocarbamates, pharmaceutical composition including noted derivatives of cyclic thiocarbamates and active ingredients of medicines as modulators of progesterone receptors |
ES2385118T3 (en) * | 2008-01-17 | 2012-07-18 | Bayer Pharma Aktiengesellschaft | Sulfoximin-substituted quinazoline derivatives as immunomodulators, their preparation and use as medicines |
EP3102567B1 (en) * | 2014-02-04 | 2019-07-17 | University of Tennessee Research Foundation | Inhibitors of paxillin function and related compositions and methods |
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US3526621A (en) * | 1966-08-03 | 1970-09-01 | Farmaceutical Italia Soc | Substituted 3,1-benzoxazin-2-one |
US3542774A (en) * | 1968-07-05 | 1970-11-24 | Warner Lambert Pharmaceutical | 3,4-dihydrobenzoxazinones |
CH624395A5 (en) * | 1976-01-08 | 1981-07-31 | Ciba Geigy Ag | |
SU843739A3 (en) * | 1978-02-17 | 1981-06-30 | Карл Томэ Гмбх (Фирма) | Method of preparing carbostyryl or oxyindole derivatives |
US4442111A (en) * | 1981-07-25 | 1984-04-10 | Dr. Karl Thomae Gesellschaft Mit Beschrankter Haftung | Antithrombotic sulfimino and sulfoximino indolinones-2 |
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1982
- 1982-05-06 DE DE19823217012 patent/DE3217012A1/en not_active Withdrawn
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1983
- 1983-04-22 EP EP83103980A patent/EP0093922B1/en not_active Expired
- 1983-04-22 DE DE8383103980T patent/DE3368621D1/en not_active Expired
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- 1983-05-02 DD DD83250508A patent/DD210453A5/en not_active IP Right Cessation
- 1983-05-02 PT PT76627A patent/PT76627B/en unknown
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- 1983-05-04 HU HU831540A patent/HU194842B/en not_active IP Right Cessation
- 1983-05-04 GR GR71308A patent/GR79255B/el unknown
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- 1983-05-04 KR KR1019830001917A patent/KR900006546B1/en not_active IP Right Cessation
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- 1983-05-05 AU AU14265/83A patent/AU563453B2/en not_active Ceased
- 1983-05-05 ES ES522104A patent/ES8402585A1/en not_active Expired
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- 1983-05-05 CA CA000427530A patent/CA1204744A/en not_active Expired
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- 1983-05-06 JP JP58079222A patent/JPS58203979A/en active Pending
- 1983-10-25 ES ES526724A patent/ES526724A0/en active Granted
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